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Self-assembling amphiphilic molecules: Synthesis in simulated interstellar/precometary ices.

Interstellar gas and dust constitute the primary material from which the solar system formed. Near the end of the hot early phase of star and planet formation, volatile, less refractory materials were transported into the inner solar system as comets and interplanetary dust particles. Once the inner planets had sufficiently cooled, late accretionary infall seeded them with complex organic compounds [Oró, J. (1961) Nature (London) 190, 389-390; Delsemme, A. H. (1984) Origins Life 14, 51-60; Anders, E. (1989) Nature (London) 342, 255-257; Chyba, C. F. & Sagan, C. (1992) Nature (London) 355, 125-131]. Delivery of such extraterrestrial compounds may have contributed to the organic inventory necessary for the origin of life. Interstellar ices, the building blocks of comets, tie up a large fraction of the biogenic elements available in molecular clouds. In our efforts to understand their synthesis, chemical composition, and physical properties, we report here that a complex mixture of molecules is produced by UV photolysis of realistic, interstellar ice analogs, and that some of the components have properties relevant to the origin of life, including the ability to self-assemble into vesicular structures.

Astronomy↗

Comet Sugano-Saigusa-Fujikawa (1983V)--a small, puzzling comet.

Spectroscopic and infrared observations of Comet Sugano-Saigusa-Fujikawa (1983V) were obtained during its close approach to the Earth on 11-14 June 1983. The [O I] production rates of 1.8 +/- 0.9 x 10(26) atoms/s observed on 12.3 June and 7 +/- 3.5 x 10(26) atoms/s on 13.4 June lead to derived water-production rates of 3 x 10(27) mol/s on 12 June and 1.1 x 10(28) mol/s on 13 June. The abundances of the minor species NH2, CN, C2, and C3 are unusually low relative to [O I]. The upper limit to the average nuclear radius from our infrared and visual photometry on 12-13 June (assuming that the entire signal came from the nucleus) is approximately 370 m. The dust/gas mass ratio was <0.01 on June 12 and <0.005 on June 13.

Astronomical Phenomena↗

On the evolution and activity of cometary nuclei.

The thermal evolution of a spherical cometary nucleus (initial radius of 2.5 km), composed initially of very cold amorphous ice and moving in comet Halley's orbit, is simulated numerically for 280 revolutions. It is found that the phase transition from amorphous to crystalline ice constitutes a major internal heat source. The transition does not occur continuously, but in five distinct rounds, during the following revolutions: 1, 7, 40-41, 110-112, and 248-252. Due to the (slow) heating of the amorphous ice between crystallization rounds, the phase transition front advances into the nucleus to progressively greater depths: 36 m on the first round, and then 91 m, 193 m, 381 m, and 605 m respectively. Each round of crystallization starts when when the boundary between amorphous and crystalline ice is brought to approximately 15 m below the surface, as the nucleus radius decreases due to sublimation. At the time of crystallization, the temperature of the transformed ice rises to 180 K. According to experimental studies of gas-laden amorphous ice, a large fraction of the gas trapped in the ice at low temperatures is released. Whereas some of the released gas may find its way out through cracks in the crystalline ice layer, the rest is expected to accumulate in gas pockets that may eventually explode, forming "volcanic calderas." The gas-laden amorphous ice thus exposed may be a major source of gas and dust jets into the coma, such as those observed on comet Halley by the Giotto spacecraft. The activity of new comets and, possibly, cometary outbursts and splits may also be explained in terms of explosive gas release following the transition from amorphous to crystalline ice.

Crystallization↗

Simultaneous multifrequency observations of Markarian 421.

The highly variable BL Lacertae object Mrk 421 has been observed simultaneously in the radio, optical ultraviolet, and X-ray bands over a period of 4 days in early 1984 December and once again in early 1985 January. Using the EXOSAT observatory, we found that dramatic changes occurred in the X-ray flux on a time scale of less than a mouth. During this time the 2-10 keV flux dropped by a factor of 8, whereas the 0.1-1 keV flux decreased by a factor of only 2. These changes were not reproduced at longer wavelengths during the period of simultaneous observations. However, a drop in the ultraviolet flux occurred some months later, which is consistent with the longer characteristic loss times for the lower energy electrons. Since the ultraviolet through radio flux is stable when the X-ray flux is changing, it is extremely unlikely that a simple synchrotron model can account for the full spectrum; in this model the whole spectrum is expected to rise uniformly and in phase as a result of the injection of energetic particles. A simple synchroton self-Compton model that is self-absorbed in the radio also requires an X-ray flux which is many orders of magnitude greater than is observed. However, this discrepancy may be explained by relativistic beaming of electrons with delta > approximately 40 or by a model in which the self-absorption turnover occurs in the optical, and the synchrotron break occurs in the X-rays. Shorter time scale (approximately 10,000 s) variability was also apparent in the 2-10 keV X-ray light curves, and we suggest that it may be a direct measure of the injection time scale. Although reasonable fits resulted when the X-ray data were compared with a simple power-law model with some absorption, a substantial improvement in chi 2 was obtained by adding a high-energy exponential cutoff. Use of this model produced a spectral index close to that typically found in the optical for BL Lacertae objects, in contrast to the high values usually inferred from X-ray spectra.

Astronomical Phenomena↗

Radiogenic heating of comets by 26Al and implications for their time of formation.

The effect of radiogenic heating on the thermal evolution of spherical icy bodies with radii 1 km < R < 100 km was investigated. The radioisotopes considered were 26Al, 40K, 232Th, 235U, and 238U. Except for the 26Al abundance, which was varied, the other initial abundances were kept fixed, at values derived from those of chondritic meteorites and corresponding to a gas-to-dust ratio of 1. The initial models were homogeneous and isothermal (To = 10 K) amorphous ice spheres, in a circular orbit at 10(4) AU from the Sun. The main object of this study was to examine the conditions under which the transition temperature from amorphous into cubic ice (Ta = 137 K) would be reached. It was shown that the influence of the short-lived radionuclide 26Al dominates the effect of other radioactive species for bodies of radii up to approximately 50 km. Consequently, if we require comets to retain their ice in amorphous form, as suggested by observations, an upper limit of approximately 4 x 10(-9) is obtained for the initial 26Al abundance in comets, a factor of 100 lower than that of the inclusions in the Allende meteorite. A lower limit for the formation time of comets may thus be derived. The possibility of a coexistence of molten cometary cores and extended amorphous ice mantles is ruled out. Larger icy spheres (R > 100 km) reached Ta even in the absence of 26Al, due to the decay of the other radionuclides. As a result, a crystalline core formed whose relative size depended on the composition assumed. Thus the outermost icy satellites in the solar system, which might have been formed of ice in the amorphous state, have probably undergone crystallization and may have exhibited eruptive activity when the gas trapped in the amorphous ice was released (e.g., Miranda).

Aluminum↗

The infrared spectrum of comet Bradfield (1987s) and the silicate emission feature.

Infrared (1-20 micrometers) observations of comet Bradfield (1987s) from three observatories are reported. Silicate emission is prominent in all the data, from heliocentric distance r=0.87 to 1.45 AU. A CVF spectrum at r=1.45 AU shows a peak at 11.3 micrometers identified as crystalline olivine; the spectral shape is similar to that in Halley. Dust optical properties are similar to those of the grains in Halley's jets. Dust production rate near perihelion was approximately 10(6) g s-1 and varied in proportion to (r-2). We suggest that some differences in grain properties among comets could result from differences in the thermal history of the nuclear surface and the relative fraction of the dust particles originating in the subsurface icy layer versus the devolatilized mantle.

Astronomical Phenomena↗

The physical and infrared spectral properties of CO2 in astrophysical ice analogs.

Both laboratory measurements and theory indicate that CO2 should be a common component in interstellar ices. We show that the exact band position, width, and profile of the solid-state 12CO2 infrared bands near 3705, 3600, 2340, and 660 cm-1 (2.70, 2.78, 4.27, and 15.2 micrometers) and the 13CO2 band near 2280 cm-1 (4.39 micrometers) are dependent on the matrix in which the CO2 is frozen. Measurements of these bands in astronomical spectra can be used to determine column densities of solid-state CO2 and provide important information on the physical conditions present in the ice grains of which the CO2 is a part. Depending on the composition of the ice, the CO2 asymmetric stretching band was observed to vary from 2328.7 to 2346.0 cm-1 and have full widths at half-maxima (FWHMs) ranging from 4.7 to 29.9 cm-1. The other CO2 bands showed similar variations. Both position and width are also concentration dependent. Absorption coefficients were determined for the five CO2 bands. These were found to be temperature independent for CO2 in CO and CO2 matrices but varied slightly with temperature for CO2 in H2O-rich ices. For all five bands this variation was found to be less than 15% from 10 to 150 K, the temperature at which H2O ice sublimes. A number of parameters associated with the physical behavior of CO2 in CO2- and H2O-rich ices were also determined. The CO2-CO2 surface binding energy in pure CO2 ices is found to be (delta Hs/k) = 2690 +/- 50 K. CO2-H2O and CO-H2O surface binding energies were determined to be (delta Hs/k) = 2860 +/- 200 K and 1740 +/- 100 K, respectively. Under our experimental conditions, CO2 condenses in measurable quantities into H2O-rich ices at temperatures up to 100 K, only slightly higher than the temperature at which pure CO2 condenses. Once frozen into an H2O-rich ice, the subsequent loss of CO2 upon warming is highly dependent on concentration. For ices with H2O/CO2 > 20, the CO is physically trapped within the H2O lattice, and little CO2 is lost until the sublimation temperature of the H2O matrix is reached. In contrast, in ices having H2O/CO2 < 5, the CO2 remains only to temperatures of about 90 K. Above this point the CO2 readily diffuses out of the H2O matrix. These results suggest that two different forms of H2O lattice are produced. The implications of these data for cometary models and our understanding of cometary formation are considered.

Astronomical Phenomena↗

Gas release in comet nuclei.

The evolution of a comet nucleus is investigated, taking into account the crystallization process by which the gas trapped in the ice is released to flow through the porous ice matrix. The equations of conservation of the energy and of the masses of ice and gas are solved throughout the nucleus, to obtain the evolution of the temperature, gas pressure and density profiles. A spherical nucleus composed of cold, porous amorphous ice, with 10% of CO trapped in it, serves as initial model. Several values of density (porosity) and pore size are considered. For each combination of parameters the model is evolved for 20-30 revolutions in comet P/Halley's orbit. Two aspects of the release of gas upon crystallization are analyzed and discussed: (a) the resulting continuous outward flux with high peaks at the time of crystallization, which is a cyclic process in the low-density models and sporadic in the high-density ones; (b) the internal pressures obtained down to depths of a few tens to approximately 200 m (depending on parameters), that are found to exceed the compressional strength of cometary ice. As a result, both cracking and explosions of the overlying ice layer and ejection of gas and ice/dust grains are expected to follow crystallization. They should appear as outbursts or sudden brightening of the comet. The model of 0.2 g cm-3 density is found to reproduce quite well many of the light-curve and activity characteristics of comet P/Halley.

Astronomical Phenomena↗

Detection of the 2165 inverse centimeter (4.619 micron) XCN band in the spectrum of L1551 IRS 5.

We report the detection of a broad absorption band at 2165 cm-1 (4.619 microns) in the spectrum of L1551 IRS 5. New laboratory results over the 2200-2100 cm-1 wavenumber interval (4.55-4.76 microns), performed with realistic interstellar ice analogs, suggest that this feature is due to a CN-containing compound. We will refer to this compound as XCN. We also confirm the presence of frozen CO (both in nonpolar and polar matrices) through absorption bands at 2140 cm-1 (4.67 microns) and 2135 cm-1 (4.68 microns). The relative abundance of solid-state CO to frozen H2O is approximately 0.13 while the abundance of XCN seems comparable to that of frozen CO.

Astronomical Phenomena↗

Condensation and vaporization studies of CH3OH and NH3 ices: major implications for astrochemistry.

In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

Ammonia↗

Crystallization of amorphous water ice in the solar system.

Electron diffraction studies of vapor-deposited water ice have characterized the dynamical structural changes during crystallization that affect volatile retention in cometary materials. Crystallization is found to occur by nucleation of small domains, while leaving a significant part of the amorphous material in a slightly more relaxed amorphous state that coexists metastably with cubic crystalline ice. The onset of the amorphous relaxation is prior to crystallization and coincides with the glass transition. Above the glass transition temperature, the crystallization kinetics are consistent with the amorphous solid becoming a "strong" viscous liquid. The amorphous component can effectively retain volatiles during crystallization if the volatile concentration is approximately 10% or less. For higher initial impurity concentrations, a significant amount of impurities is released during crystallization, probably because the impurities are trapped on the surfaces of micropores. A model for crystallization over long timescales is described that can be applied to a wide range of impure water ices under typical astrophysical conditions if the fragility factor D, which describes the viscosity behavior, can be estimated.

Astronomical Phenomena↗

The possible formation of a hydrogen coma around comets at large heliocentric distances.

An observational test--the detection of a hydrogen coma around comets at large heliocentric distances--is proposed for determining whether comets were formed by the agglomeration of unaltered, ice-coated, interstellar grains. Laboratory experiments showed that amorphous water ice traps H2, D2, and Ne below 20 K and does not release them completely until the ice is heated to 150 K. Gas/ice ratios as high as 0.63 are obtainable. Thus, if the ice-coated interstellar grains were not heated above approximately 110 K, prior to their agglomeration into cometary nuclei, the inward propagating heat waves should release from the comets a continuous flux of molecular hydrogen. This flux would exceed that of water molecules at approximately 3 AU preperihelion and approximately 4 AU postperihelion.

Astronomical Phenomena↗

Insoluble organic material of the Orgueil carbonaceous chondrite and the unidentified infrared bands.

Deuterium abundance measurements and the 13C NMR spectrum of the HF/HCl insoluble residue of the Orgueil carbonaceous chondrite indicate the presence of an extensive component of polycyclic aromatic hydrocarbons (PAH) that is of possible interstellar origin or is similar to PAH hypothesized to exist in interstellar space. Infrared spectra have been obtained using an FTIR spectrometer of the acid insoluble residue, the residue after heating in vacuum, and condensate. Bulk acid insoluble residue was pressed into KBr pellets and also heated under high vacuum to sublimate a volatile component onto KBr disks. The remaining non-volatile organic component of the Orgueil meteorite from such evaporations pressed into KBr pellets exhibits a spectral signature similar to that observed in emission from the Orion Nebula and found in Raman spectra of interplanetary dust particles (IDPs). In addition it has an 11.3 microns (885 cm-1) band indicating PAH having single hydrogens per peripheral aromatic ring. We conclude the nonvolatile material is similar to interstellar PAH because the observed 11.3 microns (885 cm-1) unidentified infrared (UIR) emission suggests interstellar PAH have single hydrogens per peripheral aromatic ring. The volatile fraction of the Orgueil shows an aliphatic CH stretch feature and its spectrum in the 2-25 microns range is similar to that of the bulk residue.

Carbon↗

Origin of the hydrocarbon component of carbonaceous chondrites: the star-meteorite connection.

We report the results of an experiment that produced a residue which closely matches the hydrocarbon component of the Murchison carbonaceous chondrite. This experiment suggests that the parent material of the meteoritic component originated as polycyclic aromatic hydrocarbon species in carbon stars during their later stages of evolution. The experiments also indicate that the pathway from those formation sites to eventual incorporation into the meteorite parent body involved hydrogenation in a plasma in the solar nebula or in H II regions prior to the solar nebula. This model is consistent with what is known about the meteoritic hydrocarbon component including deuterium abundance, the observation of cosmic infrared emission bands best attributed to polycyclic aromatic hydrocarbon molecules, and the inherent stability of these molecules that allows their formation in stars and subsequent survival in the interstellar medium.

Astronomical Phenomena↗

Explosion of comet Shoemaker-Levy 9 on entry into the Jovian atmosphere.

We use the astrophysical hydrocode ZEUS to compute high-resolution models of the disruption and deceleration of cometary fragments striking Jupiter. We find that simple analytic and semianalytic models work well for kilometer-size impactors. We show that previous numerical models that placed the explosion much deeper in the atmosphere failed to fully resolve important gasdynamical instabilities. These instabilities tear the comet apart, greatly increase its effective cross section, and bring it to an abrupt halt. A 1 km diameter fragment loses over 90% of its kinetic energy within a single scale height at an atmospheric pressure of order 10 bars. For all practical purposes, it explodes.

Algorithms↗

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices.

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

Deuterium↗

Constraints on the nucleus and dust properties from mid-infrared imaging of comet Hyakutake.

We use Mie scattering theory to determine the expected thermal emission from dust grains in cometary comae and apply these results to mid-infrared images of comet Hyakutake (C/1996 B2) obtained preperihelion in 1996 March. Calculations were performed for dust grains in the size range from 0.1 to 10 micrometers for two different compositions: amorphous olivine (a silicate glass) and an organic residue mixture. The resulting emission efficiencies are complicated functions of wavelength and particle size and are significantly different for the two materials in question. The Hyakutake data set consists of three nights of high-resolution imaging (100-150 km pixel-1 at the comet) of the inner coma at 8.7, 11.7, 12.5, and 19.7 micrometers. Attempts to fit the observed colors (ratios of fluxes at different wavelengths) using a single grain composition failed. However, fits to the data were achieved for all three nights using a mixture of approximately 1 micrometer olivine grains and approximately 7 micrometers organic grains. The resulting olivine mass fraction was between 8% and 16% of the total dust mass-loss rate. We also estimate the radius of the nucleus to be r = 2.1 +/- 0.4 km.

Astronomy↗

HCO+ imaging of comet Hale-Bopp (C/1995 O1).

The HCO+ J = 1-0 rotational transition at 89.189 GHz has been mapped in comet Hale-Bopp (C/1995 O1) over a total of 38 individual days spanning the period 1997 March 10-June 20 with the Five College Radio Astronomy Observatory 14 m antenna. HCO+ is detectable over an extended region of the comet, with the peak emission commonly located 50,000-100,000 km in the antisolar direction. Maps made throughout the apparition show significant variability in the structure of the HCO+ coma, sometimes on timescales of several hours. The HCO+ brightness is usually depressed at the nucleus position, and on some occasions, the emission is spread into a ring around the position of the nucleus. Individual spectra within the maps display broad (approximately 4 km s-1) lines redshifted by 1-2 km s-1 or more from the nominal velocity of the nucleus, with the redshift typically increasing in the antisolar direction. The spectra and maps may be generally explained by models in which the ions are accelerated tailward at a rate on the order of 10 cm s-2, provided that HCO+ is destroyed within 50,000-100,000 km of the nucleus.

Astronomy↗