Formation of H2 on amorphous ice grains and their importance for planetary atmospheres

The mechanism and the rate of formation of H₂ molecules from adsorbed H atoms on interstellar ice grains (or on ice coated non-icy grains) are investigated assuming that the ice is not crystalline but amorphous. Using the available theory and experimental data it is concluded that, in contrast to crystalline grains, the mobility of the adsorbed atoms on amorphous grains at temperatures of 10–20 K is exceedingly low so that the controlling factor is the probability that two H atoms are accidentally adsorbed within a site or two of each other. The rate of H₂ formation on ice grains per unit volume is much lower than previously estimated and is very sensitive to temperature. This conclusion applies not only to pure amorphous ice investigated here, but also to impure ice and to other grains (carbon or silicates) which would not be crystalline, such as graphite, but may be highly imperfect or actually amorphous aggregates of atoms or molecules.It is further shown that the presence of amorphous ice and clathrate grains in the early solar system would play a significant role in our understanding of the compositional anomalies in the Earth's atmosphere. The lifetime of these grains would be strongly affected by the absence of crystallinity.Invited contribution to the Proceedings of a Workshop onThermodynamics and Kinetics of Dust Formation in the Space Medium held at the Lunar and Planetary Institute, Houston, 6–8 September, 1978.     

Interstellar catalysis

Although it is generally accepted that most, if not all, of the molecular hydrogen in interstellar space is formed through recombination reactions on grains, the exact mechanism by which this is accomplished is far from certain. In the past, great emphasis had been placed on the physical adsorption of H atoms on cold dielectric grains and their subsequent recombination and desorption as H₂ molecules. However, a careful re-examination of the problem leads us to believe that a rate coefficient ofk10^–17 cm³ s^–1—the value usually quoted in the literature—is a very strong overestimate. The same thing can be said for the recombination of H atoms on graphite grains. Since two-body gas phase reactions are not sufficient by themselves to account for the observed abundances of H₂, an alternate mechanism must exist. It is suggested that the chemisorption of hydrogen on transition metal grains may be just that formation mechanism. After separating the adsorption rate equations from those of desorption and using experimentally determined parameters, it is shown that transition metal grains can successfully catalyze as much H₂ as the theoretical maximum predicted for cold ice grains, even though metal grains are probably less than 10% as abundant (by mass) than dielectrics.     

The influence of grain mantles on the formation of hydrogen molecules on grain surfaces

The physical adsorption energy,E, of hydrogen molecules on various substrates at temperatures between 5 and 30 K and at the lowest practicable gas densities has been measured. Values ofE/k are for condensed CO 340 K, CO₂ 800 K, H₂O 850 K and for ‘dirty’ graphite 980 K and ‘dirty’ copper 800 K. From these measurements temperature ranges in which H atoms might combine on the surface to form H₂ molecules are estimated. Duley has discussed the formation and composition of condensed gas mantles on interstellar grains. The effects of such mantles in promoting and poisoning hydrogen molecule formation are discussed.     

Model for surface reactions on interstellar grains — A numerical study

A model of the formation of molecules by surface reactions on interstellar grains is described and assessed numerically. The model predicts that for the molecules—other than H₂-likely to be important in the interstellar medium, the formation rates by surface reactions are insensitive to the nature of the surface. The formation rates have magnitudes which are significant when compared with other routes. The model also describes H₂ formation in high density clouds and shows it to be parameter dependent.     

Synthesis of hydrogen peroxide in water ice by ion irradiation

We present infrared absorption studies on the effects of 50-100 keV Ar⁺ and 100 keV H⁺ ion irradiation of water ice films at 20-120 K. The results support the view that energetic ions can produce hydrogen peroxide on the surface of icy satellites and rings in the outer Solar System, and on ice mantles on interstellar grains. The ion energies are characteristic of magnetospheric ions at Jupiter, and therefore the results support the idea that radiolysis by ion impact is the source of the H₂O₂ detected on Europa by the Galileo infrared spectrometer. We found that Ar⁺ ions, used to mimic S⁺ impacts, are roughly as efficient as H⁺ ions in producing H₂O₂, and that 100 keV H⁺ ions can produce hydrogen peroxide at 120 K. The synthesized hydrogen peroxide remained stable while warming the ice film after irradiation; the column density of the formed H₂O₂ is constant until the ice film begins to desorb, but the concentration of H₂O₂ increases with time during desorption because the water sublimes at a faster rate. Comparing the shape of the 3.5-μm absorption feature of H₂O₂ to the one measured on Europa shows excellent agreement in both shape and position, further indicating that the H₂O₂ detected on Europa is likely caused by radiolysis of water ice.     

Equilibrium temperatures of interstellar iron grains

Because of the relatively low number densities found in typical interstellar clouds, molecules observed there must be produced by a combination of both two-body gas-phase reactions and surface reactions. The latter type includes various catalytic reactions, such as the formation of H₂ on transition metal grains. These reactions are very temperature dependent, the grain temperature appearing in the exponential of the rate equations. Because of the small heat capacities of the grains due to their small sizes, they may be subject to considerable fluctuations in temperature. This problem is examined for iron grains and found to be minimal for sizes greater than 100 Å. Steady-state equilibrium temperatures are then calculated for a size distribution of iron particles ranging from 10³ to 10⁹ atoms per grain by a refined method of an earlier work by one of us (RGT). The results are that iron grain temperatures are significantly greater than those of dielectric grains of comparable size in the same radiation field.     

Chemical evolution of the gas in C-type shocks in dark clouds

A magnetohydrodynamic model of a steady, transverse C-type shock in a dense molecular cloud is presented. A complete gas–grain chemical network is taken into account: the gas-phase chemistry, the adsorption of gas species on dust grains, various desorption mechanisms, the grain surface chemistry, the ion neutralization on dust grains, the sputtering of grain mantles. The population densities of energy levels of ions CI, CII and OI and molecules H₂, CO, H₂O are computed in parallel with the dynamical and chemical rate equations. The large velocity gradient approximation is used in the line radiative transfer calculations. The simulations consist of two steps: (i) modelling of the chemical and thermal evolution of a static molecular cloud and (ii) shock simulations. A comparison is made with the results of publicly available models of similar physical systems.The focus of the paper is on the chemical processing of gas material and ice mantles of dust grains by the shock. Sputtering of ice mantles takes place in the shock region close to the temperature peak of the neutral gas. At high shock speeds, molecules ejected from ice mantles are effectively destroyed in hot gas, and their survival time is low—of the order of dozens of years. After a passage of high-speed C-type shock, a zone of high abundance of atomic hydrogen appears in the cooling postshock gas that triggers formation of complex organic species such as methanol. It is shown that abundances of some complex organic molecules (COMs) in the postshock region can be much higher than in the preshock gas. These results are important for interpretation of observations of COMs in protostellar outflows.     

Trapping and release of gases by water ice and implications for icy bodies

The trapping and release of H₂, CO, CO₂, CH₄, Ar, Ne, and N₂ by amorphous water ice was studied experimentally under dynamic conditions, at low temperatures starting at 16°K, with gas pressure of 5 × 10^?8?10^?6 Torr. CO, CH₄, Ar, and N₂ were found to be released in three or four distinct temperature ranges, each resulting from a different trapping mechanism: (a) 30–55°K, where the gas frozen on the water ice evaporates; (b) 135–155°K, where gas is squeezed out of the water ice during the transformation of amorphous ice to cubic ice; (c) 165–190°K, where gas and water are released simultaneously, probably by the evaporation of a clathrate hydrate, and, occasionally (d) 160–175°K, where deeply buried gas is released during the transformation of cubic ice to hexagonal ice. If the third range is indeed due to clathrate formation, CO was found to form this compound. CO₂ did not form a clathrate under the experimental conditions. Excess hydrogen did not affect the occlusion of other gases. Hydrogen itself was trapped only at 16°K. Neon was not trapped at 25°K. With cubic ice, the only trapping mechanism is freezing of gas on the ice surface. No fractionation between the gas phase and the ice was observed with a mixture of CO and Ar. Massive ejection of ice grains was observed during the evaporation of the gas in three (a,c,d) out of the four ranges. The experimental results are used to explain several cometary phenomena, especially those occurring at large heliocentric distances, and are applied also to Titan's atmospheric composition and to the possible ejection of ice grains from Enceladus.     

An in situ study of presolar grains and the fine-grained matrices of the Meteorite Hills 00526 and Queen Alexandra Range 97008 unequilibrated ordinary chondrites

Here we report in situ structural and chemical analyses of four presolar grains and the matrices of the Meteorite Hills (MET) 00526 L3.05 and Queen Alexandra Range (QUE) 97008 L3.05 unequilibrated ordinary chondrites (UOCs). The presolar grains in MET 00526 include one Fe-rich single crystal olivine, and one olivine grain that contains both amorphous and polycrystalline material. The single crystal olivine likely has origins in the circumstellar envelope (CSE) of a red giant branch (RGB) or asymptotic giant branch (AGB) star, and the amorphous/polycrystalline olivine has an O-isotopic composition consistent with origins in a type II supernova. The presolar grains from QUE 97008 are Fe rich and include one crystalline, stoichiometric olivine that contains a Ca-rich core and one crystalline, stoichiometric pyroxene grain, both of which have O-isotopic compositions consistent with origins in the CSEs of low-mass AGB/RGB stars. The matrices of both UOCs are mineralogically diverse with evidence for unaltered material in the form of amorphous silicates and a C-rich nanoglobule and altered material in the form of Ni-rich sulfides, abundant Fe-rich olivine, and Fe-Mg zoning in matrix silicates. No phyllosilicates were observed. The Fe-rich olivine grains are the dominant alteration phase in both UOCs and likely replaced primary amorphous silicates in the presence of an Fe-rich fluid during parent body alteration. Our work suggests that the ordinary and carbonaceous chondrites received a similar inventory of dust with comparable structures and chemistries.     

Interstellar water and interstellar ice

There are two ways that water ice can form in the interstellar medium: H₂O molecules can form in the gas phase and then freeze out onto dust grain surfaces, or O and OH can be converted at the surfaces of grains to form H₂O, which is then retained. Bergin et al. (1998) have recently shown that shocks passing through interstellar clouds sufficiently frequently can make the first method effective. However, we present results from a similar chemical model which indicate that this requires significant optical shielding because of the high ionization fraction in regions exposedto a high UV flux. We deduce, therefore, that grain surface reactions probably represent the main source of H₂O ice on lines of sight with visual extinction up to about 6 magnitudes to an embedded source or 12 magnitudes to a background object. This revised version was published online in July 2006 with corrections to the Cover Date.     

Molecular hydrogen in intercloud medium

We discuss the formation of molecular hydrogen on the surfaces of grains in a hot intercloud medium, by the process of chemisorption of hydrogen atoms on graphite grains. It is suggested that the molecular hydrogen observed towards stars with low reddening, may be located in the intercloud medium towards these stars. A comparison of the observed population distributions of H₂ with the theoretical calculations shows that the observations are in the main consistent with a gas kinetic-temperature 8000 K and densities about 0.1 to 1 cm^–3, parameters which are appropriate to the intercloud phase of the two phase model of the interstellar medium.Tata Institute of Fundamental Research, Bombay, India     

Pressure dependent trace gas trapping in amorphous water ice at 77 K: Implications for determining conditions of comet formation

The nature of cometary volatile materials is subject to debate. Theoretical models of cometary nuclei and laboratory studies suggest that these objects could be made of amorphous water ice in addition to other volatile molecules and refractory grains. This water ice structure has the ability to encapsulate the gases of surrounding environment, reflecting the physical and chemical conditions during their deposition. Therefore, the knowledge of the chemical composition of volatile molecules trapped in amorphous water ice provides a tool for probing the formation environment of cometary ice grains. Experimental studies of gas trapping efficiency in amorphous water ice have been previously conducted mostly under kinetic conditions, where dynamic pumping and temperature gradients prevented rigorous calibrations. In this work, we investigated the trapping efficiencies of Ar, CO, CH₄, Kr and N₂ by depositing water vapor as ice in the presence of trace gases in a volume submerged in liquid nitrogen at 77 K. The gas trapping efficiencies were determined simply by monitoring the pressure difference of the trace gases before and after the deposition of a known amount of water molecules as amorphous ice.Our results show that the trapped gas to water molecule ratio in amorphous ice is controlled primarily by the partial pressure of the gas during water ice deposition, and is independent of the ice deposition rate as well as the gas to water ratio in the vapor phase. The trapping efficiencies of gases decrease in the order of Kr > CH₄ > CO > Ar > N₂ in accordance with previous studies. Assuming that the water ice structure of comets is at least partially amorphous water ice at the time of their formation, these results suggest that the total pressure and composition of the surrounding environment of amorphous ice formation are significant controlling factors of trace gas concentrations in cometary ice. This further indicates that the evolution of the solar nebula and timing of cometary ice condensation can also be important parameters in linking the volatile contents of comets and their formation process.     

Chemical effects of H2 formation excitation

The effects of the production on dust grain surfaces of molecular hydrogen in excited states have been investigated. On the assumption that all of the H₂ formed on the surface of grains has a sufficient level of excitation too vercome the energy barriers in the formation reactions for the important OH and CH⁺ radicals, we consider the likely abundances of excited H₂ (H₂ ^*), OH and CH⁺ in various situations. Two different models are employed; the first links the H₂ ^* abundance directly to that of H₂ using a steady-state approximation, whilst the second considers the time-dependence of H₂ ^*. The second model is applied to gas that has been subjected to a strong isothermal shock (specifically, the shock-induced collapse of a diffuse cloud), which results in an extreme (high density, high atomic hydrogen abundance) environment. In general, it is found that the presence of the excited H₂ has only marginal effects on the chemistry of interstellar clouds. However, in the isothermal shock model, the abundances of CH⁺ are significantly enhanced, but only on short timescales, whilst the effects on the OH abundances are smaller, but last longer. We conclude that other than in such exceptional environments there are no obvious chemical signatures of the formation of H₂ ^*. This revised version was published online in July 2006 with corrections to the Cover Date.     

Crystalline comet dust: Laboratory experiments on a simple silicate system

Abstract— Spectra for certain comets show the presence of crystalline silicate dust grains believed to have been incorporated during comet formation. While grain crystallization is widely assumed to result from the thermal annealing of precursor amorphous grains, the physical processes behind the silicate amorphous‐to‐crystalline transition are poorly understood. This makes it difficult to place constraints on the evolutionary histories of both grains and comets, and consequently, on the nebular conditions in which they formed. It has, therefore, become necessary to study this process in the laboratory using simulated grain materials. In this paper, we discuss recent results from laboratory investigations into a basic amorphous MgSiO₃ silicate annealed in the region of 1000 K. Our object is not to model the behavior of dust grains per se, but to study the underlying process of crystallization and separate the physics of the material from the astrophysics of dust grains. In our experiments, we bring together spectroscopic measurements made in the infrared with the high resolution structural probing capabilities of synchrotron X‐ray powder diffraction. The combined use of these complementary techniques provides insights into the crystallization process that would not be easily obtained if each was used in isolation. In particular, we focus on the extent to which the identification of certain spectral features attributed to crystalline phases extends to the physical structure of the grain material itself. Specifically, we have identified several key features in the way amorphous MgSiO₃ behaves when annealed. Rather than crystallize directly to enstatite (MgSiO₃) structures, in crystallographic terms, amorphous MgSiO₃ can enter a mixed phase of crystalline forsterite (Mg₂SiO₄) and SiO₂‐rich amorphous silicate where structural evolution appears to stall. Spectroscopically, the evolution of the 10 μm band does not appear to correlate directly with structural evolution, and therefore, may be a poor indicator of the degree of crystallinity. Indeed, certain features in this band may not be indicators of crystal type. However, the 20 μm band is found to be a good indicator of crystal structure. We suggest that forsterite forms from the ordering of pre‐existing regions rich in SiO₄ and that this phase separation is aided by a dehydrogenation processes that results in the evolutionary stall. The implications of this work regarding future observations of comets are discussed.     

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.     

The role of submicrometer aerosols and macromolecules in H2 formation in the titan haze

Previous studies of the photochemistry of small molecules in Titan’s atmosphere found it difficult to have hydrogen atoms removed at a rate sufficient to explain the observed abundance of unsaturated hydrocarbons. One qualitative explanation of the discrepancy nominated catalytic aerosol surface chemistry as an efficient sink of hydrogen atoms, although no quantitative study of this mechanism was attempted. In this paper, we quantify how haze aerosols and macromolecules may efficiently catalyze the formation of hydrogen atoms into H₂. We describe the prompt reaction model for the formation of H₂ on aerosol surfaces and compare this with the catalytic formation of H₂ using negatively charged hydrogenated aromatic macromolecules. We conclude that the PRM is an efficient mechanism for the removal of hydrogen atoms from the atmosphere to form H₂ with a peak formation rate of ∼ 70 cm⁻³ s⁻¹ at 420 km. We also conclude that catalytic H₂ formation via hydrogenated anionic macromolecules is viable but much less productive (a maximum of ∼ 0.1 cm⁻³ s⁻¹ at 210 km) than microphysical aerosols.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

The effect of ammonia ice on the outgoing thermal radiance from the atmosphere of Jupiter

We examine the effects of NH₃ ice particle clouds in the atmosphere of Jupiter on outgoing thermal radiances. The cloud models are characterized by a number density at the cloud base, by the ratio of the scale height of the vertical distribution of particles (H_p) to the gas scale height (H_g), and by an effective particle radius. NH₃ ice particle-scattering properties are scaled from laboratory measurements. The number density for the various particle radius and scale height models is inferred from the observed disk average radiance at 246 cm^?1, and preliminary lower limits on particle sizes are inferred from the lack of apparent NH₃ absorption features in the observed spectral radiances as well as the observed minimum flux near 2100 cm^?1. We find lower limits on the particle size of 3 μm if H_p/H_g = 0.15, or 10μmif H_p/H_g = 0.50 or 0.05. NH₃ ice particles are relatively dark near the far-infrared and 8.5-μm atmospheric windows, and the outgoing thermal radiances are not very sensitive to various assumptions about the particle-scattering function as opposed to radiances at 5 μm, where particles are relatively brighter. We examined observations in these three different spectral window regions which provide, in principle, complementary constraints on cloud parameters. Characterization of the cloud scale height is difficult, but a promising approach is the examination of radiances and their center-to-limb variation in spectral regions where there is significant opacity provided by gases of known vertical distribution. A blackbody cloud top model can reduce systematic errors due to clouds in temperature sounding to the level of 1K or less. The NH₃ clouds provide a substantial influence on the internal infrared flux field near the 600-mbar level.     

The size distribution of dust grains in single clouds – II. The analysis of extinction using inhomogeneous grains

The extinction curves of single clouds, seen towards the stars HD 147165, 179406 and 202904, have been modelled using various mixtures containing both the bare and inhomogeneous (composite and/or multilayer) grains. It has been shown that the models composed of the bare graphite and silicate grains together with the multilayer grains containing silicates, organic refractory and water ice, are more useful in explaining extinction under the reduced cosmic abundances. The models based on Mathis' composite grains or on Greenberg & Li's core-mantle grains can also provide quite good fits of the extinction and the measured scattering parameters, but still require an excessive amount of carbon which results in too large a C/O ratio. The inhomogeneous grains essentially contribute to the extinction in practically the whole wavelength range of our extinction curves. As a rule, such grains have quite wide size distributions, centred at around 100 nm, although graphite grains are mainly of small sizes.     

Enhanced CO2 trapping in water ice via atmospheric deposition with relevance to Mars

It has been suggested that inclusions of CO₂ or CO₂ clathrate hydrates may comprise a portion of the polar deposits on Mars. Here we present results from an experimental study in which CO₂ molecules were trapped in water ice deposited from CO₂/H₂O atmospheres at temperatures relevant for the polar regions of Mars. Fourier-Transform Infrared spectroscopy was used to monitor the phase of the condensed ice, and temperature programmed desorption was used to quantify the ratio of species in the generated ice films. Our results show that when H₂O ice is deposited at 140-165 K, CO₂ is trapped in large quantities, greater than expected based on lower temperature studies in amorphous ice. The trapping occurs at pressures well below the condensation point for pure CO₂ ice, and therefore this mechanism may allow for CO₂ deposition at the poles during warmer periods. The amount of trapped CO₂ varied from 3% to 16% by mass at 160 K, depending on the substrate studied. Substrates studied were a tetrahydrofuran (C₄H₈O) base clathrate and Fe-montmorillonite clay, an analog for Mars soil. Experimental evidence indicates that the ice structures are likely CO₂ clathrate hydrates. These results have implications for the CO₂ content, overall composition, and density of the polar deposits on Mars.