Evolution of Interstellar Ices

Infrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Ices in molecular clouds are dominated by the very simple molecules H₂O, CH₃OH, NH₃, CO, CO₂, and probably H₂CO and H₂. More complex species including nitriles, ketones, and esters are also present, but at lower concentrations. The evidence for these, as well as the abundant, carbon-rich, interstellar, polycyclic aromatic hydrocarbons (PAHs) is reviewed. Other possible contributors to the interstellar/pre-cometary ice composition include accretion of gas-phase molecules and in situ photochemical processing. By virtue of their low abundance, accretion of simple gas-phase species is shown to be the least important of the processes considered in determining ice composition. On the other hand, photochemical processing does play an important role in driving dust evolution and the composition of minor species. Ultraviolet photolysis of realistic laboratory analogs readily produces H₂, H₂CO, CO₂, CO, CH₄, HCO, and the moderately complex organic molecules: CH₃CH₂OH (ethanol), HC(=O)NH₂ (formamide), CH₃C(=O)NH₂ (acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C₆H₁₂N₄), as well as more complex species including amides, ketones, and polyoxymethylenes (POMs). Inclusion of PAHs in the ices produces many species similar to those found in meteorites including aromatic alcohols, quinones and ethers. Photon assisted PAH-ice deuterium exchange also occurs. All of these species are readily formed and are therefore likely cometary constituents. This revised version was published online in June 2006 with corrections to the Cover Date.     

Rare Atoms,Molecules and Radicals in the Coma of P/Halley

We have searched for rare molecules and radicals in the coma of P/Halley using the ion data obtained by IMS-Giotto. Whereas our established methods were used in the ionosphere, a new model was developed for the interpretation of the ion data in the outer coma. Ne/H₂O < 1.5 × 10^-3 was determined in the coma of the comet. Upper limits for the production of Na were derived from the very low abundance of Na⁺. Methyl cyanide and (probably) ethyl cyanide were identified with abundances of CH₃CN/H₂O = (1.4 ± .6) × 10^-3 and C₂H₅CN/H₂O = (2.8 ± 1.6) × 10^-4. These results and upper limits for other N-bearing species confirm that nitrogen is depleted in the Halley material. C₄H was identified and a point source strength of C₄H/H₂O = (2.3 ± .8) × 10^-3 was derived. Our upper limit for C₃H is lower than the abundance of C₄H. This is in agreement with the enhanced abundances of C_nH species with even numbers of C-atoms found in interstellar molecular clouds, suggesting that the C₄H in Halley was synthesized under molecular cloud conditions. Thus, C₄H and other organics with unpaired electrons may turn out to be indicators for a molecular cloud origin of cometary constituents. This revised version was published online in June 2006 with corrections to the Cover Date.     

Local Interstellar Parameters as They Are Inferred from Analysis of Observations Inside the Heliosphere

This paper provides a brief summary on the current knowledge of the properties of the Circum-Heliospheric Interstellar Medium (CHISM). It discusses what can be learnt on the parameters of CHISM’s components from analysis of measurements performed inside the heliosphere. The analysis is based on the kinetic-gasdynamic models of the solar wind/interstellar medium interaction. We focus the analysis on three types of diagnostics: 1) interstellar H atom number density at the heliospheric termination shock inferred from pickup ion measurements, 2) the location and time of the Voyager 1 and 2 termination shock crossings, 3) the deflection of the interstellar H atom flow inside the heliosphere as been measured by SOHO/SWAN. From these results estimations of the unknown local interstellar parameters are deduced. The parameters are the number densities of interstellar H⁺ and H and the magnitude and direction of the interstellar magnetic field in the vicinity of the solar system.     

The Solar System d/h Ratio: Observations and Theories

The measured D/H ratios in interstellar environments and in the solar system are reviewed. The two extreme D/H ratios in solar system water - (720±120)×10⁻⁶ in clay minerals and (88±11)×10⁻⁶ in chondrules, both from LL3 chondritic meteorites - are interpreted as the result of a progressive isotopic exchange in the solar nebula between deuterium-rich interstellar water and protosolar H₂. According to a turbulent model describing the evolution of the nebula (Drouart et al., 1999), water in the solar system cannot be a product of thermal (neutral) reactions occurring in the solar nebula. Taking 720×10⁻⁶ as a face value for the isotopic composition of the interstellar water that predates the formation of the solar nebula, numerical simulations show that the water D/H ratio decreases via an isotopic exchange with H₂. During the course of this process, a D/H gradient was established in the nebula. This gradient was smoothed with time and the isotopic homogenization of the solar nebula was completed in 10⁶ years, reaching a D/H ratio of 88×10⁻⁶. In this model, cometary water should have also suffered a partial isotopic re-equilibration with H₂. The isotopic heterogeneity observed in chondrites result from the turbulent mixing of grains, condensed at different epochs and locations in the solar nebula. Recent isotopic determinations of water ice in cold interstellar clouds are in agreement with these chondritic data and their interpretation (Texeira et al., 1999). This revised version was published online in June 2006 with corrections to the Cover Date.     

The Time-of-Flight Energy,Angle, Mass Spectrograph (Teams) Experiment for Fast

The Time-of-flight Energy Angle Mass Spectrograph (TEAMS) is being flown on the FAST Small Explorer mission to measure the 3-dimensional distribution function of the major ion species present in the lower magnetosphere. The instrument is similar to time-of-flight plasma analyzer systems that have been designed and planned for flight as CODIF (COmposition and DIstribution Function analyzer) on the four European Space Agency Cluster-II spacecraft and, as ESIC (Equator-S Ion Composition instrument) on Equator-S. This instrument allows the 3-dimensional distribution functions of individual ion species to be determined within spin period (2.5 s). Two-dimensional distributions are measured in 80 ms. These capabilities are crucial for the study of selective energization processes in the auroral regions of the magnetosphere. The design, operational characteristics, and test and calibration results for this instrument are presented. The sensor consists of a toroidal top-hat electrostatic analyzer with instantaneous acceptance of ions over 360° in polar angle. After post-acceleration of the incoming ions by up to 25 kV, a time-of-flight mass spectrograph discriminates the individual species. It has been demonstrated through calibration that the instrument can easily separate H⁺, He²⁺, He⁺, O⁺ and, for energies after post-acceleration of > 20 keV, even O₂ ⁺ molecules. On-board mass discrimination and the internal accumulation of several distinct data quantities combined with the spacecraft's flexible telemetry formatting allow for instrument data rates from 7.8 kb s^–1 to 315 kb s^–1 to be telemetered to ground through the FAST centralized Instrument Data Processor.     

Spectroscopy Between the Stars

The emission and absorption spectra of interstellar molecules are reviewed with special consideration of recent observational and technical advances in the shorter submillimeter wave region of the electromagnetic spectrum. Single-dish observations have contributed in the past probably most of the information about the structure of interstellar molecular clouds. At present about 120 interstellar molecules have been identified in interstellar clouds and circumstellar envelopes, evidence of a rich and diversified chemistry. CO, the most abundant interstellar molecule and other diatomic molecules and radicals are found throughout molecular clouds, whereas the more complex molecules are found in high-density cores, which are often the sites of active star formation. These locations represent prime targets for the search for larger molecules, such as glycine. The ignition of young stars is accompanied by strong heating of the surrounding material by radiation and/or shocks, leading to photoevaporation of molecules depleted on dust grains driving a "hot core" chemistry, traceable by its rich organic chemistry and its prevailing high excitation conditions (up to about 2000 cm^-1). However, in the list of detected interstellar molecules many simple hydrides are still missing, e.g. SH, PH, PH₂, etc., which constitute the building blocks for larger molecules. With the technological opening of the terahertz region (ν ∼1 THz corresponds to λ ∼0.3 mm) to both laboratory and interstellar spectroscopy, great scientific advances are to be expected. Amongst these will be the direct detection of the lowest rotational transitions of the light hydrides, the low energy bending vibrations of larger (linear) molecules, and possibly the ring-puckering motion of larger ring molecules such as the polycyclic (multiring) aromatic hydrocarbons. This revised version was published online in June 2006 with corrections to the Cover Date.     

Isotopic Fractionation by Ion-Molecule Reactions

Isotopic fractionation in interstellar clouds can occur by ion-molecule reactions at low temperatures. The major effect is not kinetic but thermodynamic in origin in that it arises from the difference in rate coefficients between forward and backward directions in reactions which exchange isotopic atoms. In this article, we concentrate on deuterium fractionation in interstellar clouds; this effect enhances the relative abundances of deuterated isotopomers to their normal counterparts by up to four orders of magnitude as compared with the basic D/H elemental abundance ratio. We also discuss the fractionation of ¹⁵N and ¹³C. This revised version was published online in August 2006 with corrections to the Cover Date.     

The ionospheres of the major planets

Physical and chemical processes which affect the equilibrium distribution of ionization in the atmospheres of Jupiter, Saturn, Uranus and Neptune are reviewed. Current models imply readily detectable ionospheres for all four planets and suggest that protons should represent the dominant positive ion. Attention is directed to the probable importance of dissociative ionization of H₂ as a source of H⁺. A number of potentially important loss mechanisms for H⁺ are discussed including a possible reaction of H⁺ with vibrationally excited H₂. Protons may be removed efficiently at lower altitudes by reaction with CH₄ and this process may offer a simple remote means for location of the turbopause.This is one of the publications by the Science Advisory Group.     

The Cool Interstellar Medium

Infrared spectroscopy and photometry with ISO covering most of the emission range of the interstellar medium has led to important progress in the understanding of the physics and chemistry of the gas, the nature and evolution of the dust grains and also the coupling between the gas and the grains. We review here the ISO results on the cool and low-excitation regions of the interstellar medium, where T _gas≲ 500 K, n _H∼ 100–10⁵ cm⁻³ and the electron density is a few 10⁻⁴. JEL codes: D24, L60, 047 Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, The Netherlands, and the United Kingdom), and with the participation of ISAS and NASA.     

The Ice Survey Opportunity of ISO

The instruments on board the Infrared Space Observatory have for the first time allowed a complete low (PHOT, CVF) to medium resolution (SWS) spectroscopic harvest, from 2.5 to 45 μm, of interstellar dust. Amongst the detected solids present in starless molecular clouds surrounding recently born stellar and still embedded objects or products of the chemistry in some mass loss envelopes, the so-called “ice mantles” are of specific interest. They represent an interface between the very refractory carbonaceous and silicates materials that built the first grains with the rich chemistry taking place in the gas phase. Molecules condense, react on ices, are subjected to UV and cosmic ray irradiation at low temperatures, participating efficiently to the evolution toward more complex molecules, being in constant interaction in an ice layer. They also play an important role in the radiative transfer of molecular clouds and strongly affect the gas phase chemistry. ISO results shed light on many other species than H₂O ice. The detection of these van der Waal's solids is mainly performed in absorption. Each ice feature observed by ISO spectrometer is an important species, with abundance in the 10⁻⁴–10⁻⁷ range with respect to H₂. Such high abundances represent a substantial reservoir of matter that, once released later on, replenishes the gas phase and feeds the ladder of molecular complexity. Medium resolution spectroscopy also offers the opportunity to look at individual line profiles of the ice features, and therefore to progressively reveal the interactions taking place in the mantles. This article will give a view on selected results to avoid to overlap with the numerous reviews the reader is invited to consult (e.g. van Dishoeck, in press; Gibb et al., 2004.). Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, The Netherlands, and the United Kingdom), and with the participation of ISAS and NASA.     

MIRO: Microwave Instrument for Rosetta Orbiter

The European Space Agency Rosetta Spacecraft, launched on March 2, 2004 toward Comet 67P/Churyumov-Gerasimenko, carries a relatively small and lightweight millimeter-submillimeter spectrometer instrument, the first of its kind launched into deep space. The instrument will be used to study the evolution of outgassing water and other molecules from the target comet as a function of heliocentric distance. During flybys of the asteroids (2867) Steins and (21) Lutetia in 2008 and 2010 respectively, the instrument will measure thermal emission and search for water vapor in the vicinity of these asteroids. The instrument, named MIRO (Microwave Instrument for the Rosetta Orbiter), consists of a 30-cm diameter, offset parabolic reflector telescope followed by two heterodyne receivers. Center-band operating frequencies of the receivers are near 190 GHz (1.6 mm) and 562 GHz (0.5 mm). Broadband continuum channels are implemented in both frequency bands for the measurement of near surface temperatures and temperature gradients in Comet 67P/Churyumov-Gerasimenko and the asteroids (2867) Steins and (21) Lutetia. A 4096 channel CTS (Chirp Transform Spectrometer) spectrometer having 180 MHz total bandwidth and 44 kHz resolution is, in addition to the continuum channel, connected to the submillimeter receiver. The submillimeter radiometer/spectrometer is fixed tuned to measure four volatile species – CO, CH₃OH, NH₃ and three, oxygen-related isotopologues of water, H₂ ¹⁶O, H₂ ¹⁷O and H₂ ¹⁸O. The basic quantities measured with the MIRO instrument are surface temperature, gas production rates and relative abundances, and velocity and excitation temperature of each species, along with their spatial and temporal variability. This paper provides a short discussion of the scientific objectives of the investigation, and a detailed discussion of the MIRO instrument system.     

Energisation of O+ and O+ 2 Ions at Mars: An Analysis of a 3-D Quasi-Neutral Hybrid Model Simulation

We have studied the loss of O⁺ and O⁺ ₂ ions at Mars with a numerical model. In our quasi-neutral hybrid model ions (H⁺, He⁺⁺, O⁺, O⁺ ₂) are treated as particles while electrons form a massless charge-neutralising fluid. The employed model version does not include the Martian magnetic field resulting from the crustal magnetic anomalies. In this study we focus the Martian nightside where the ASPERA instrument on the Phobos-2 spacecraft and recently the ASPERA-3 instruments on the Mars Express spacecraft have measured the proprieties of escaping atomic and molecular ions, in particular O⁺ and O⁺ ₂ ions. We study the ion velocity distribution and how the escaping planetary ions are distributed in the tail. We also create similar types of energy-spectrograms from the simulation as were obtained from ASPERA-3 ion measurements. We found that the properties of the simulated escaping planetary ions have many qualitative and quantitative similarities with the observations made by ASPERA instruments. The general agreement with the observations suggest that acceleration of the planetary ions by the convective electric field associated with the flowing plasma is the key acceleration mechanism for the escaping ions observed at Mars.     

Observation of Injection and Pre-Acceleration Processes in the Slow Solar Wind

Knowledge of injection and pre-acceleration mechanisms of ions is of fundamental importance for understanding particle acceleration that takes place in various astrophysical settings. The heliosphere offers the best chance to study these poorly understood processes experimentally. We examine ion injection and pre-acceleration using measurements of the bulk and suprathermal solar wind, and pickup ions. Our most puzzling observation is that high-velocity tails, extending to at least 60 keV/e - the upper limit of measurements -, are omnipresent in the slow, in-ecliptic solar wind; these tails exist even in the absence of any shocks. The cause of these tails is unknown. In the disturbed solar wind inside CIRs and downstream of shocks and waves these high-speed tails in the distributions of H⁺, He⁺ and He⁺⁺ become more pronounced and more complex, but with the shapes of the tails showing the same dependence on ion speed for the different species. Pickup hydrogen and helium are found to be readily injected for subsequent acceleration to MeV energies, and thus are the dominant source of CIR-accelerated energetic ions. Competing sources of MeV ions heavier than He are: (1) heated suprathermal solar wind observed downstream of CIR shocks, (2) interstellar N, O and Ne, and (3) the newly discovered heavy pickup ions from an extended inner source inside 1 AU. Our main conclusion is that mechanisms other than the traditional first-order shock acceleration process produce most of the modestly accelerated ions seen in the slow solar wind. This revised version was published online in August 2006 with corrections to the Cover Date.     

Numerical analysis of hypersonic thermochemical non-equilibrium environment for an entry configuration in ionized flow

A theoretical methodology for thermochemical non-equilibrium flow combing with the HLLC (Harten-Lax-van Leer Contact) scheme was applied to study the hypersonic thermochemical non-equilibrium environment of an entry configuration in ionized flow. A two-temperature controlling model was utilized and the Gupta’s 11 species (N₂, O₂, NO, O, N, NO⁺, N₂⁺, O₂⁺, N⁺, O⁺, e^?) thermochemical non-equilibrium model was taken. Firstly, numerical calculations of hypersonic thermochemical non-equilibrium environments for different aerodynamic shapes were carried out to verify the reliability of the method above. Then, the method was used to research the effects of ionization and wall catalysis on the hypersonic thermochemical non-equilibrium environment of the entry configuration in ionized flow. The shock stand-off distance can be reduced by thermochemical reactions but doesn’t continue to decrease significantly when ionization occurs. The shock stand-off distance calculated by the 11 species model is 4.2% smaller than that calculated by the 5 species (N₂, O₂, NO, O, N) thermochemical non-equilibrium model without considering ionization. Ionization reduces wall heat flux but increases wall pressure a little. The effect of ionization on aerothermal loads is greater than that of aerodynamic loads. The thermochemical reactions of electrons and ions catalyzed at the wall increase wall heat flux significantly but make a small change in wall pressure. The maximum wall heat flux obtained by only considering the electrons and ions catalyzed at the partially catalytic wall condition is 11.8% less than that calculated at the super-catalytic wall condition.     

Aeronomy of Extra-Solar Giant Planets

The intense stellar UV radiation field incident upon extra-solar giant planets causes profound changes to their upper atmospheres. Upper atmospheric temperatures can be tens of thousands of kelvins, causing thermal dissociation of H₂ to H. The stellar ionizing flux converts H to H⁺. The high temperatures also drive large escape rates of H, but for all but the planets with the smallest orbits, this flux is not large enough to affect planet evolution. The escape rate is large enough to drag off heavier atoms such as C and O. For very small orbits, when the hill sphere is inside the atmosphere, escape is unfettered and can affect planet evolution.     

Ignition enhancement of ethylene/air by NOx addition

Recently, non-equilibrium plasma assisted combustion (PAC) has been found to be promising in reducing the ignition delay time in hypersonic propulsion system. NO x produced by non-equilibrium plasma can react with intermediates during the fuel oxidation process and thereby has influence on the combustion process. In this study, the effects of NO x addition on the ignition process of both the homogeneous ethylene/air mixtures and the non-premixed diffusion layer are examined numerically. The detailed chemistry for ethylene oxidization together with the NO x sub-mechanism is included in the simulation. Reaction path analysis and sensitivity analysis are conducted to give a mechanistic interpretation for the ignition enhancement by NO x addition. It is found that for both the homogenous and non-premixed ignition processes at normal and elevated pressures, NO 2 addition has little influence on the ignition delay time while NO addition can significantly promote the ignition process. The ignition enhancement is found to be caused by the promotion in hydroxyl radical production which quickly oxidizes ethylene. The promotion in hydroxyl radical production by NO addition is achieved in two ways:one is the direct production of OH through the reaction HO2+NO = NO2+OH, and the other is the indirect production of OH through the reactions NO+O2=NO2+O and C2H4+O = C2H3+OH. Moreover, it is found that similar to the homogeneous ignition process, the acceleration of the diffusion layer ignition is also controlled by the reaction HO2+NO = NO2+OH.     

An ISO View on Interstellar and Cometary Ice Chemistry

The ISO-SWS instrument offering a large wavelength coverage and a resolution well adapted to the solid phase has changed our knowledge of the physical-chemical properties of ices in space. The discovery of many new ice features was reported and the comparison with dedicated laboratory experiments allowed the determination of more accurate abundances of major ice components. The presence of CO₂ ice has recently been confirmed with the SWS (Short Wavelength Spectrometer) as a dominant ice component of interstellar grain mantles. The bending mode of CO₂ ice shows a particular triple-peak structure which provides first evidence for extensive ice segregation in the line-of-sight toward massive protostars. A comparison of interstellar and cometary ices using recent ISO data and ground-based measurements has revealed important similarities but also indicated that comets contain, beside pristine interstellar material, admixtures of processed material. The investigation of molecules in interstellar clouds is essential to reveal the link between dust in the interstellar medium and in the Solar System. This revised version was published online in June 2006 with corrections to the Cover Date.     

Dynamics of magnetospheric ion Composition as observed by the GEOS mass spectrometer

After one year of operation the GEOS-1 Ion Composition Experiment has surveyed plasma composition at all local times in the L range 3 8 and the energy per charge range from thermal to 16 keV/e. From measurements made in the keV range during eleven magnetic storms we find that the percentage of heavy (M/Q > 1) ions present in the outer magnetosphere increases by a factor of 3 to 10 during disturbances. We conclude that two independent sources (solar wind, characterized by ⁴He²⁺, and ionosphere, characterized by O⁺) give on the average comparable contributions to injected populations, although in a single event one or the other source may dominate. However, in magnetically quiet periods protons are the dominant species with a few percent of heavy ions. With the help of special satellite manoeuvres magnetic field aligned fluxes of 0.05-3 keV/e H⁺, He⁺, O⁺ with traces of O²⁺ have been observed which may be related to ion beams found previously at lower altitudes in the auroral zone. At still lower energies ( 1 eV/e) the thermal plasma population is found to be made up of six ion species, three of which, D⁺, He²⁺ and O²⁺, were unknown in the magnetosphere prior to the GEOS-1 measurements. We present here a study of the evolution of doubly charged ions and their parent populations over four consecutive days. Various production mechanisms for doubly charged ions are discussed. We argue that ionization of singly charged ions by UV and energetic electrons and protons is the dominant process for plasmasphere production. Furthermore, the observed high concentrations of O²⁺ at high altitudes are a result of production in the upper ionosphere and plasmasphere combined with upward transport by thermal diffusion. Throughout the 1 year lifetime of GEOS-1 the ICE functioned perfectly and, because of its novel design, a short review of technical performance is included here.     

溶胶共凝法制备准连续密度梯度SiO2气凝胶

针对气凝胶在航空航天领域的应用需求,为了进一步拓展单一密度气凝胶的应用范围,对密度梯度SiO2气胶的制备进行了研究.采用自建密度梯度制备成型装置,以正硅酸乙酯为有机硅源,经溶胶共凝工艺,结合CO2超临干燥技术,获得密度范围在60~160 mg/cm3的准连续密度梯度SiO2气凝胶.采用光学显微镜、扫描电子显微镜、X线相...     

A Comparative Study of the Influence of the Active Young Sun on the Early Atmospheres of Earth, Venus, and Mars

Because the solar radiation and particle environment plays a major role in all atmospheric processes such as ionization, dissociation, heating of the upper atmospheres, and thermal and non-thermal atmospheric loss processes, the long-time evolution of planetary atmospheres and their water inventories can only be understood within the context of the evolving Sun. We compare the effect of solar induced X-ray and EUV (XUV) heating on the upper atmospheres of Earth, Venus and Mars since the time when the Sun arrived at the Zero-Age-Main-Sequence (ZAMS) about 4.6 Gyr ago. We apply a diffusive-gravitational equilibrium and thermal balance model for studying heating of the early thermospheres by photodissociation and ionization processes, due to exothermic chemical reactions and cooling by IR-radiating molecules like CO₂, NO, OH, etc. Our model simulations result in extended thermospheres for early Earth, Venus and Mars. The exospheric temperatures obtained for all the three planets during this time period lead to diffusion-limited hydrodynamic escape of atomic hydrogen and high Jeans’ escape rates for heavier species like H₂, He, C, N, O, etc. The duration of this blow-off phase for atomic hydrogen depends essentially on the mixing ratios of CO₂, N₂ and H₂O in the atmospheres and could last from ∼100 to several hundred million years. Furthermore, we study the efficiency of various non-thermal atmospheric loss processes on Venus and Mars and investigate the possible protecting effect of the early martian magnetosphere against solar wind induced ion pick up erosion. We find that the early martian magnetic field could decrease the ion-related non-thermal escape rates by a great amount. It is possible that non-magnetized early Mars could have lost its whole atmosphere due to the combined effect of its extended upper atmosphere and a dense solar wind plasma flow of the young Sun during about 200 Myr after the Sun arrived at the ZAMS. Depending on the solar wind parameters, our model simulations for early Venus show that ion pick up by strong solar wind from a non-magnetized planet could erode up to an equivalent amount of ∼250 bar of O⁺ ions during the first several hundred million years. This accumulated loss corresponds to an equivalent mass of ∼1 terrestrial ocean (TO (1 TO ∼1.39×10²⁴ g or expressed as partial pressure, about 265 bar, which corresponds to ∼2900 m average depth)). Finally, we discuss and compare our findings with the results of preceding studies.