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PubMed2004

Dual column capillary gas chromatographic system for the in situ analysis of volatile organic compounds on a cometary nucleus.

Two Wall Coated Open Tubular capillary columns, coated with poly(cyanopropylphenyl-dimethyl)siloxane and poly(diphenyl-dimethyl)siloxane stationary phases, have been selected for use in the COmetary SAmpling and Composition space experiment for the separation and identification of the wide range of volatile organic compounds which could be present in cometary nuclei. This article presents the main characteristics of the tandem column system for the analysis of solutes of cometary interest within the constraints of space instrumental operating conditions. The high efficiency of the columns is demonstrated and the influence of the operating conditions on their separation properties are investigated. The studied columns exhibit complementary retention pattern: their use in a dual column system makes it possible to achieve the separation and the identification of the compounds of interest. Finally, the good analytical behavior of the columns when analyzing samples which include large amounts of water, the main presumed volatile in comets, is demonstrated. The presented results thus show the suitability of the selected tandem columns system for the desired analyses, and their performance on adaptation to in-situ cometary chemical investigation.

Chromatography, Gas↗
PubMedDate not supplied

Compound-specific isotope analysis of the organic constituents in carbonaceous chondrites.

The carbonaceous chondrite meteorites contain evidence of the formation of the solar system, part of which is present within organic matter. In recent years, compound-specific isotope analysis (CSIA) has been useful in deciphering this complex record. The current published data set provides an insight into the source environments and reaction mechanisms that have contributed to the final state of the organic constituents in carbonaceous chondrites. This review summarises the CSIA data and related key interpretations.

Carbon Compounds, Inorganic↗
PubMed2004

Assignment of quinone derivatives as the main compound class composing 'interstellar' grains based on both polarity ions detected by the 'Cometary and Interstellar Dust Analyser' (CIDA) onboard the spacecraft STARDUST.

The 'Cometary and Interstellar Dust Analyser' (CIDA) is a particle impact time-of-flight mass spectrometer onboard the NASA spacecraft STARDUST. A series of positive and negative ion mass spectra from the impact of (apparently) interstellar dust particles has been collected since 1999. In the meantime laboratory work has been performed to better understand the ion formation processes of organic grains impacting at those speeds (>15 km/s) and to relate them to some other ion formation methods. The key ion types were the negative ions, with some additional information from the positive ions. Here, first the principal ion formation rules are briefly reviewed. Secondly, the common substance class is inferred mainly by the application of exclusion principles, and appears to be partly condensed aromatic and quinonoid compounds with high oxygen and low nitrogen content. Oxygen appears to be present in quinone-type structures with condensed aromatic rings, possibly with furan substructures and some hydroxyl moieties. Some nitrogen may be present in pyrrole- or quinoline-type structures. Considerations of thermodynamics and radiation physics of these dust particles within the solar system are consistent with this interpretation. Quinoenzyme cofactors such as the known compound pyrroloquinoline-quinone (PQQ) and its subconstituents would be expected to yield similar mass spectra.

Dust↗
PubMed1993

Secondary processing of chondrules and refractory inclusions (CAIs) by gasdynamic heating.

A theoretical model of aerodynamic heating of a meteoric particle upon entry into a parent body atmosphere is presented. The model includes the effects of melting, vaporization, and heat conduction into the particle interior. Properties of chondrule rims are interpreted in the context of the model. We conclude that the formation of true melt rims by atmospheric entry requires that a low-melting-temperature component be fractionated in the outer part of the chondrule prior to rim formation, and that the range of thermal alteration effects observed in UOC chondrites reflects the variety of encounter conditions and chondrite types. Further tests of the model are suggested.

Atmosphere↗
PubMed1993

An experimental study of the organic molecules produced in cometary and interstellar ice analogs by thermal formaldehyde reactions.

Thermally promoted formaldehyde (H2CO) reactions in very low temperature ices have been studied to test their importance as a source of organic molecules in astrophysical environments such as comets and interstellar ices. The infrared absorption strengths of a number of the H2CO bands were measured in 10 K ices of pure H2CO and H20:H2CO = 100:3. Infrared spectroscopy was used to monitor the formaldehyde chemistry during warm-up of ices containing H2CO and one or more of the molecules H2O, CH3OH, CO, CO2, O2, and NH3. Formaldehyde reactions do not proceed at low temperatures in the absence of NH3. However, even small traces of NH3 (NH3/H2CO > or = 0.005) are sufficient to induce conversion of a considerable fraction (> 40%) of the H2CO into organic residues. Formaldehyde reactions were observed to start at temperatures as low as 40 K for NH3:H2CO binary ices and at approximately 80 K in astrophysically relevant (i.e., H2O-dominated) ices. A total of five different organic products of these reactions can be distinguished by infrared spectroscopy. One of them is polyoxymethylene (POM), a well-known H2CO polymerization product, whereas the others are reaction products of H2CO with H20, CH3OH and NH3. These all seem to be derivatives of polyoxymethylene. The nature of the components and their relative abundances depend strongly on the initial composition of the ice mixture as well as on the ice's irradiation history. We estimate that about 1% of the organics found in the coma of Comet Halley could have been produced by thermal formaldehyde reactions taking place in the nucleus.

Ammonia↗
PubMed1993

What can meteorites tell us about nebular conditions and processes during planetesimal accretion?

Analysis of the most primitive meteorites can yield detailed information about environmental conditions and physical/chemical processes in the earliest Solar System, including the nebular stage during which planetesimals were accreted. Such information pertains to time scales, thermal and chemical evolution, inhomogeneity and mixing, magnetic fields, and grain growth in the solar nebula. Nebular processes identified include evaporation, condensation, localized melting, and fractionation both of solids from gas and among different solids. Little direct evidence remains even in primitive meteorites of the actual accretion process. The absence of intrinsic factors capable of enhancing accretion among meteoritic constituents suggests that gravitational instabilities might have been important in promoting planetesimal accretion.

Chemical Phenomena↗
PubMed1993

Hydrothermal processing of cometary volatiles--applications to Triton.

Subsequent to its capture by Neptune, Triton could have experienced an episode of tidal heating sufficient to melt its icy mantle and possibly its rocky core as well. This heating would have driven hydrothermal circulation at the core-rock/mantle-ocean boundary. We consider the chemical consequences of this hydrothermal reprocessing on Triton's volatile budget by assuming an initial cometary composition for the icy mantle and evaluating the effects of changes in temperature and oxidation state. We assume that the latter would have been controlled by mineral assemblages in the rock. Such reprocessing could explain the lack of carbon monoxide in the atmosphere of Triton and its depletion relative to N2 and (apparently) CO2 in the satellite's surface ices. Our calculations also show that whatever the original source of nitrogen in Triton, N2 and/or NH3 are likely abundant products of hydrothermal reprocessing. Depending on the temperature and prevailing oxidation state, acetic acid, ethanol, urea, methanol, and ethanamine are possible important components, in addition to ammonia, of the resulting mantle material. Triton may thus preserve the organic chemistry that might have led to the origin of life in early terrestrial hydrothermal systems.

Ammonia↗
PubMed1994

The collision of Jupiter and Comet Shoemaker-Levy 9.

A simple description of the disruption and deceleration of 100-m- to 5-km-diameter comets striking Jupiter is combined with numerical simulations of the subsequent explosions to predict the fate of Comet Shoemaker-Levy 9. Kilometer-size objects of density 1 g/cm3 explode at about the 10-bar level; a fragment of the same diameter but of density 0.3 g/cm3 explodes at about the 2-bar level. Detailed numerical simulations of the first 3 min of the explosion were performed using the astrophysical hydrodynamics program ZEUS-3D. Our numerical simulations begin either with hot cylinders with dimensions suggested by the disruption and deceleration model or with an initial wake constructed from a moving line charge. In all cases, extensive plumes of hot gas are expelled from the atmosphere. The models with wakes evolve about twice as fast as the initially confined models. Models of both types generate similar pressure waves into the planet. Temperatures and negative hydrogen ion opacities were computed by solving a battery of Saha equations. For atmospheric entry, light curves were computed assuming thermal radiation by clean jovian air with a surface area consistent with the (changing) cross-sectional area of the impactor. On entry the largest bolides could be very bright, possibly as bright as Jupiter for observers placed to see them, although for kilometer-size impactors the luminosity peak is obscured by clouds. The timescale is about 10 sec. For the fireball, light curves were computed from the numerical simulations assuming a grey atmosphere. Metals from the vaporized comet provide electrons that dramatically increase the opacity of Jovian air at low temperature; the resulting effective radiating temperature of the fireball is of order 3000 K. The fireball rises through and above the atmosphere, brightening at first as its surface area increases, but later fading to invisibility as its temperature drops and its opacity plummets. The timescale is about 100 sec.

Astronomy↗
PubMed1995

Comets, impacts, and atmospheres.

We are proposing a model for the delivery of volatiles to the inner planets by icy planetesimals (comets). Laboratory studies of the trapping of gases in ice forming at low temperatures simulate the formation of comet nuclei at various distances from the Sun in the solar nebula. The total gas content as well as the relative proportions of gases trapped in the ice are strong functions of temperature. As they trap N2 inefficiently, all planetesimals formed interior to Neptune are deficient in nitrogen, acquiring values of C/N resembling those found in the inner planet volatile inventories. A mixture of three basic types of comets appears capable of accounting for the observed volatile inventories on Venus, Earth, and Mars, with the caveat that impact erosion is necessary to explain the present condition of the martian atmosphere. The model includes the possibility of several epochs of clement conditions on early Mars. Some tests of these ideas are suggested, including measurements in Jupiter's atmosphere by the Galileo probe.

Atmosphere↗
PubMed1997

Biological potential of extraterrestrial materials. 2. Microbial and plant responses to nutrients in the Murchison carbonaceous meteorite.

Meteoritic materials are investigated as potential early planetary nutrients. Aqueous extracts of the Murchison C2 carbonaceous meteorite are utilized as a sole carbon source by microorganisms, as demonstrated by the genetically modified Pseudomonas fluorescence equipped with the lux gene. Nutrient effects are observed also with the soil microorganisms Nocardia asteroides and Arthrobacter pascens that reach populations up to 5 x 10(7) CFU/ml in meteorite extracts, similar to populations in terrestrial soil extracts. Plant tissue cultures of Asparagus officinalis and Solanum tuberosum (potato) exhibit enhanced pigmentation and some enhanced growth when meteorite extracts are added to partial nutrient media, but inhibited growth when added to full nutrient solution. The meteorite extracts lead to large increases in S, Ca, Mg, and Fe plant tissue contents as shown by X-ray fluorescence, while P, K, and Cl contents show mixed effects. In both microbiological and plant tissue experiments, the nutrient and inhibitory effects appear to be best balanced for growth at about 1:20 (extracted solid : H2O) ratios. The results suggest that solutions in cavities in meteorites can provide efficient concentrated biogenic and early nutrient environments, including high phosphate levels, which may be the limiting nutrient. The results also suggest that carbonaceous asteroid resources can sustain soil microbial activity and provide essential macronutrients for future space-based ecosystems.

Arthrobacter↗
PubMed1998

Cratering rates on the Galilean satellites.

We exploit recent theoretical advances toward the origin and orbital evolution of comets and asteroids to obtain revised estimates for cratering rates in the jovian system. We find that most, probably more than 90%, of the craters on the Galilean satellites are caused by the impact of Jupiter-family comets (JFCs). These are comets with short periods, in generally low-inclination orbits, whose dynamics are dominated by Jupiter. Nearly isotropic comets (long period and Halley-type) contribute at the 1-10% level. Trojan asteroids might also be important at the 1-10% level; if they are important, they would be especially important for smaller craters. Main belt asteroids are currently unimportant, as each 20-km crater made on Ganymede implies the disruption of a 200-km diameter parental asteroid, a destruction rate far beyond the resources of today's asteroid belt. Twenty-kilometer diameter craters are made by kilometer-size impactors; such events occur on a Galilean satellite about once in a million years. The paucity of 20-km craters on Europa indicates that its surface is of order 10 Ma. Lightly cratered surfaces on Ganymede are nominally of order 0.5-1.0 Ga. The uncertainty in these estimates is about a factor of five. Callisto is old, probably more than 4 Ga. It is too heavily cratered to be accounted for by the current flux of JFCs. The lack of pronounced apex-antapex asymmetries on Ganymede may be compatible with crater equilibrium, but it is more easily understood as evidence for nonsynchronous rotation of an icy carapace.

Astronomical Phenomena↗
PubMed1999

An experimental study of the isotopic enrichment in Ar, Kr, and Xe when trapped in water ice.

The isotopic enrichment of argon, krypton, and xenon, when trapped in water ice, was studied experimentally. The isotopes were found to be enriched according to their (m1/m2)1/2 ratio. These enrichment factors could be useful for comparison among the uncertain cosmic or solar isotopic ratios, the hopeful in situ cometary ratio, and those in Earth's atmosphere, in the context of cometary delivery of volatiles to Earth.

Argon↗
PubMed1987

Airborne and groundbased spectrophotometry of comet P/Halley from 5-13 micrometers.

Spectrophotometry from 5-10 micrometers (delta lambda/lambda approximately 0.02) of comet Halley was obtained from the Kuiper Airborne Observatory on 1985 December 12.1 and 1986 April 8.6 and 10.5, UT. 8-13 micrometers data were obtained on 17.2 December 1985 from the Nickel Telescope at Lick Observatory. The spectra show a strong broad emission band at 10 micrometers and a weak feature at 6.8 micrometers. We do not confirm the strong 7.5 micrometers emission feature observed by the Vega 1 spacecraft. The 10 micrometers band, identified with silicate materials, has substructure indicative of crystalline material. The band can be fitted by combining spectra data from a sample of interplanetary dust particles. The primary component of the silicate emission is due to olivine. The 6.8 micrometers emission feature can be due either to carbonates or the C-H deformation mode in organic molecules. The lack of other emission bands is used to place limits on the types of organic molecules responsible for the emission observed by others at 3.4 micrometers. Color temperatures significantly higher than the equilibrium blackbody temperature indicate that small particles are abundant in the coma. Significant spatial and temporal variations in the spectrum have been observed and show trends similar to those observed by the spacecraft and from the ground. Temporal variability of the silicate emission relative to the 5-8 micrometers continuum suggests that there are at least two physically separated components of the dust.

Astronomical Phenomena↗
PubMed1987

Infrared emission from P/Halley's dust coma during March 1986.

2 to 20 micrometers photometry of the inner dust coma of comet Halley was obtained at the NASA IRTF on Mar 6.85, 12.8, 13.75, 17.7, and 24.8. Positions offset 10" were measured as well as the central brightness. The strength of the 10 micrometers emission feature was observed to vary with location in the coma. The infrared emission is in general agreement with the dust size distribution measured from the Vega and Giotto spacecraft. Mar 6.8, 17.7, and 24.8 corresponded to strong dust jet activity. The strength of the 10 micrometers silicate emission is shown to be a sensitive indicator of grain size and thus of jet activity. Dust production rate on March 13.75, 6 h before Giotto encounter, was approximately 10(7) gm s-1.

Astronomy↗
PubMed1987

The dust distribution within the inner coma of comet P/Halley 1982i: encounter by Giotto's impact detectors.

Analysis of the data from Giotto's Dust Impact Detection System experiment (DIDSY) is presented. These data represent measurement of the size of dust grains incident on the Giotto dust shield along its trajectory through the coma of comet P/Halley on 1986 March 13/14. First detection occurred at some 287000 km distance from the nucleus on the inbound leg; the majority of the DIDSY subsystems remained operational after closest approach (604 km) yielding the last detection at about 202000 km from the nucleus. In order to improve the data coverage (and especially for the smallest grains, to approximately 10(-19) kg particle mass), data from the PIA instrument has been combined with DIDSY data. Flux profiles are presented for the various mass channels showing, to a first approximation, a 1/R2 flux dependence, where R is the distance of the detection point from the cometary nucleus, although significant differences are noted. Deviations from this dependence are observed, particularly close to the nucleus. From the flux profiles, mass and geometrical area distributions for the dust grains are derived for the trajectory through the coma. Groundbased CCD imaging of the dust continuum in the inner coma at the time of encounter is also used to derive the area of grains intercepted by Giotto. The results are consistent with the area functions derived by Giotto data and the low albedo of the grains deduced from infrared emission. For the close encounter period (-5 min to +5 min), the cumulative mass distribution function has been investigated, initially in 20 second periods; there is strong evidence from the data for a steepening of the index of the mass distribution for masses greater than 10(-13) kg during passage through dust jets which is not within the error limits of statistical uncertainty. The fluences for dust grains along the entire trajectory is calculated; it is found that extrapolation of the spectrum determined at intermediate masses (cumulative mass index alpha = 0.85) is not able to account for the spacecraft deceleration as observed by the Giotto Radio Science Experiment and by ESOC tracking operations. Data at large masses (>10(-8) kg) recently analysed from the DIDSY data set show clear evidence of a decrease in the mass distribution index at these masses within the coma, and it is shown that such a value of the mass index can provide sufficient mass for consistency with the observed deceleration. The total particulate mass output from the nucleus of comet P/Halley at the time of encounter would be dependent on the maximum mass emitted if this change in slope observed in the coma were also applicable to the emission from the nucleus; this matter is discussed in the text. The flux time profiles have been converted through a simple approach to modeling of the particle trajectories to yield an indication of nucleus surface activity. There is indication of an enhancement in flux at t approximately -29 s corresponding to crossing of the dawn terminator, but the flux detected prior to crossing of the dawn terminator is shown to be higher than predicted by simple modelling. Further enhancements corresponding to jet activity are detected around +190 s and +270 s.

Astronomical Phenomena↗
PubMed1987

Observations of HCN in comet P/Halley.

We present observations of the HCN J = 1-0 rotational transition at 3.4 mm wavelength in comet P/Halley. The data were obtained during a total of 56 individual observing sessions between November 1985 and May 1986 and represent the first time that a cometary parent molecule has been so extensively monitored. The HCN production rate is well correlated with the total visual magnitude of the comet, and comparison of the HCN production to the total gas production of the comet indicates that it is a relatively minor constituent with 0.1% the abundance of H2O. Comparison of HCN and CN production suggests that HCN is a major parent molecule of CN, but probably not the sole parent. HCN spectra obtained by binning the data with heliocentric distance show that the line width, and thus the parent outflow velocity, increases with decreasing heliocentric distance, and that there is a tendency for the lines to be blue shifted due to anisotropic outgassing from the nucleus. Finally, there is evidence of day-to-day time variability in the total HCN emission and in the hyperfine ratios. The time variation of the total emission is consistent with the known time variable behavior of the comet, and detailed comparisons to optical data, where possible, confirm this interpretation. However, non-LTE values of the hyperfine ratios are not consistent with theoretical modeling of the excitation of these transitions.

Astronomical Phenomena↗
PubMed1987

Evidence for methane and ammonia in the coma of comet P/Halley.

Methane and ammonia abundances in the coma of Halley are derived from Giotto IMS data using an Eulerian model of chemical and physical processes inside the contact surface to simulate Giotto HIS ion mass spectral data for mass-to-charge ratios (m/q) from 15 to 19. The ratio m/q = 19/18 as a function of distance from the nucleus is not reproduced by a model for a pure water coma. It is necessary to include the presence of NH3, and uniquely NH3, in coma gases in order to explain the data. A ratio of production rates Q(NH3)/Q(H2O) = 0.01-0.02 results in model values approximating the Giotto data. Methane is identified as the most probable source of the distinct peak at m/q = 15. The observations are fit best with Q(CH4)/Q(H2O) = 0.02. The chemical composition of the comet nucleus implied by these production rate ratios is unlike that of the outer planets. On the other hand, there are also significant differences from observations of gas phase interstellar material.

Ammonia↗