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.     

Rheological and Thermal Properties of Icy Materials

Laboratory measurements of physical properties of planetary ices generate information for dynamical models of tectonically active icy bodies in the outer solar system. We review the methods for measuring both flow properties and thermal properties of icy planetary materials in the laboratory, and describe physical theories that are essential for intelligent extrapolation of data from laboratory to planetary conditions. This review is structured with a separate and independent section for each of the two sets of physical properties, rheological and thermal. The rheological behaviors of planetary ices are as diverse as the icy moons themselves. High-pressure water ice phases show respective viscosities that vary over four orders of magnitude. Ices of CO₂, NH₃, as well as clathrate hydrates of CH₄ and other gases vary in viscosity by nearly ten orders of magnitude. Heat capacity and thermal conductivity of detected/inferred compositions in outer solar system bodies have been revised. Some low-temperature phases of minerals and condensates have a deviant thermal behavior related to paramount water ice. Hydrated salts have low values of thermal conductivity and an inverse dependence of conductivity on temperature, similar to clathrate hydrates or glassy solids. This striking behavior may suit the dynamics of icy satellites.     

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.     

Radiolysis and Photolysis of Icy Satellite Surfaces: Experiments and Theory

The transport and exchange of material between bodies in the outer solar system is often facilitated by their exposure to ionizing radiation. With this in mind we review the effects of energetic ions, electrons and UV photons on materials present in the outer solar system. We consider radiolysis, photolysis, and sputtering of low temperature solids. Radiolysis and photolysis are the chemistry that follows the bond breaking and ionization produced by incident radiation, producing, e.g., O₂ and H₂ from irradiated H₂O ice. Sputtering is the ejection of molecules by incident radiation. Both processes are particularly effective on ices in the outer solar system. Materials reviewed include H₂O ice, sulfur-containing compounds (such as SO₂ and S₈), carbon-containing compounds (such as CH₄), nitrogen-containing compounds (such as NH₃ and N₂), and mixtures of those compounds. We also review the effects of ionizing radiation on a mixture of N₂ and CH₄ gases, as appropriate to Titan’s upper atmosphere, where radiolysis and photolysis produce complex organic compounds (tholins).     

On the Prediction of CO Outgassing from Comets Hale-Bopp and Wirtanen

The gas flux from a volatile icy-dust mixture is computed using a comet nucleus thermal model in order to study the evolution of CO outgassing during several apparitions from long-period Comet Hale-Bopp and short-period Comet Wirtanen. The comet model assumes a spherical, porous body containing a dust component, one major ice component (H₂O), and one minor ice component of higher volatility (CO). The initial chemical composition is assumed to be homogeneous. The following processes are taken into account: heat and gas diffusion inside the rotating nucleus; release of outward diffusing gas from the comet nucleus; chemical differentiation by sublimation of volatile ices in the surface layers and recondensation of gas in deeper, cooler layers. A 2-D time dependent solution is obtained through the dependence of the boundary conditions on the local solar illumination as the nucleus rotates. The model for Comet Hale-Bopp was compared with observational measurements (Biver et al., 1999). The best agreement was obtained for a model with amorphous water ice and CO, assuming that a part of the latter is trapped by the water ice, another part is condensed as an independent ice phase. The model confirms that sublimation of CO ice at large heliocentric distance produces a gradual increase in the comet's activity as it approaches the Sun. Crystallization of amorphous water ice begins at 7 AU from the Sun, but no outbursts were found. Seasonal effects and thermal inertia of the nucleus material lead to larger CO outgassing rates as the comet recedes from the Sun. In the second part of this work the model was run with the orbital parameters of Comet Wirtanen. Unlike Comet Hale-Bopp, the predicted CO outgassing from Comet Wirtanen is almost constant throughout its orbit. Such behavior can be explained by a thermally evolved and chemically differentiated comet nucleus. This revised version was published online in June 2006 with corrections to the Cover Date.     

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.     

Morphological Structure and Chemical Composition of Cometary Nuclei and Dust

The chemical composition of comet nuclei derived from current data on interstellar dust ingredients and comet dust and coma molecules are shown to be substantially consistent with each other in both refractory and volatile components. When limited by relative cosmic abundances the water in comet nuclei is constrained to be close to 30% by mass and the refractory to volatile ratio is close to 1:1. The morphological structure of comet nuclei, as deduced from comet dust infrared continuum and spectral emission properties, is described by a fluffy (porous) aggregate of tenth micron silicate core-organic refractory mantle particle on which outer mantles of predominantly H₂O ices contain embedded carbonaceous and polycyclic aromatic hydrocarbon (PAH) type particles of size in the of 1 - 10nm range. This revised version was published online in June 2006 with corrections to the Cover Date.     

Long Term Climate Records from Polar Ice

One of the great challenges in climate research is to investigate the principal mechanisms that control global climatic changes and an effective way to learn more about it, is the reconstruction of past climate changes. The most important sources of information about such changes and the associated composition of the atmosphere are the two large ice caps of Greenland and Antarctica. Analysis of ice cores is the most powerful means we have to determine how climate has changed over the last few climatic cycles, and to relate this to changes in atmospheric composition, in particular to concentrations of the principal greenhouse gases – CO₂, CH₄ and N₂O (carbon dioxide, methane, and nitrous oxide).Transitions from cold ice age climates to warmer interstadials have always been accompanied by an increase of the atmospheric concentration of the three principal greenhouse gases. This increase has been, at least for CO₂, vital for the ending of glacial epochs. A highly simplified course of events for the past four transitions would then be as follows: first, changing orbital parameters initiated the end of the glacial epoch; second, an increase in greenhouse gases then amplified the weak orbital signal; third, in the second half of the transition, warming was further amplified by decreasing albedo, caused by melting of the large ice sheets in the Northern Hemisphere going parallel with a change of the ocean circulation.The isotopic records of Greenland ice cores show evidence for fast and drastic climatic changes during the last glacial epoch. Possible causes and mechanisms of such changes and their significance as global climatic events are discussed here. Ice core results also enable the reaction of the environment to past global changes to be investigated.It will also be discussed how reliable stable isotope records are as a local temperature proxy and how representative paleoclimatic results from Greenland and Antarctica are in relation to global climate.     

Formation of Giant Planets– An Attempt in Matching Observational Constraints

We present models of giant planet formation, taking into account migration and disk viscous evolution. We show that migration can significantly reduce the formation timescale bringing it in good agreement with typical observed disk lifetimes. We then present a model that produces a planet whose current location, core mass and total mass are comparable with the one of Jupiter. For this model, we calculate the enrichments in volatiles and compare them with the one measured by the Galileo probe. We show that our models can reproduce both the measured atmosphere enrichments and the constraints derived by Guillot et al. (2004), if we assume the accretion of planetesimals with ices/rocks ratio equal to 4, and that a substantial amount of CO₂ was present in vapor phase in the solar nebula, in agreement with ISM measurements.     

Emergence of a Habitable Planet

We address the first several hundred million years of Earth’s history. The Moon-forming impact left Earth enveloped in a hot silicate atmosphere that cooled and condensed over ∼1,000 yrs. As it cooled the Earth degassed its volatiles into the atmosphere. It took another ∼2 Myrs for the magma ocean to freeze at the surface. The cooling rate was determined by atmospheric thermal blanketing. Tidal heating by the new Moon was a major energy source to the magma ocean. After the mantle solidified geothermal heat became climatologically insignificant, which allowed the steam atmosphere to condense, and left behind a ∼100 bar, ∼500 K CO₂ atmosphere. Thereafter cooling was governed by how quickly CO₂ was removed from the atmosphere. If subduction were efficient this could have taken as little as 10 million years. In this case the faint young Sun suggests that a lifeless Earth should have been cold and its oceans white with ice. But if carbonate subduction were inefficient the CO₂ would have mostly stayed in the atmosphere, which would have kept the surface near ∼500 K for many tens of millions of years. Hydrous minerals are harder to subduct than carbonates and there is a good chance that the Hadean mantle was dry. Hadean heat flow was locally high enough to ensure that any ice cover would have been thin (<5 m) in places. Moreover hundreds or thousands of asteroid impacts would have been big enough to melt the ice triggering brief impact summers. We suggest that plate tectonics as it works now was inadequate to handle typical Hadean heat flows of 0.2–0.5 W/m². In its place we hypothesize a convecting mantle capped by a ∼100 km deep basaltic mush that was relatively permeable to heat flow. Recycling and distillation of hydrous basalts produced granitic rocks very early, which is consistent with preserved >4 Ga detrital zircons. If carbonates in oceanic crust subducted as quickly as they formed, Earth could have been habitable as early as 10–20 Myrs after the Moon-forming impact.     

On the Flux of Water and Minor Volatiles from the Surface of Comet Nuclei

Surface temperature and the available effective energy strongly influence the mass flux of H₂O and minor volatiles from the nucleus. We perform computer simulations to model the gas flux from volatile, icy components in porous ice-dust surfaces, in order to better understand results from observations of comets. Our model assumes a porous body containing dust, one major ice component (H₂O) and up to eight minor components of higher volatility (e.g. CO, CH₄, CH₃OH, HCN, C₂H₂, H₂S), The body's porous structure is modeled as a bundle of tubes with a given tortuosity and an initially constant pore diameter. Heat is conducted by the matrix and carried by the vapors. The model includes radially inward and outward flowing vapor within the body, escape of outward flowing gas from the body, complete depletion of less volatile ices in outer layers, and recondensation of vapor in deeper, cooler layers. From the calculations we obtain temperature profiles and changes in relative chemical abundances, porosity and pore size distribution as a function of depth, and the gas flux into the interior and into the atmosphere for each of the volatiles at various positions of the body in its orbit. In this paper we relate the observed relative molecular abundances in the coma of Comet C/1995 O1 (Hale-Bopp) and of Comet 46P/Wirtanen to molecular fluxes at the surface calculated from our model. This revised version was published online in June 2006 with corrections to the Cover Date.     

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.     

Deuterium Fractionation in Interstellar Clouds

This paper reviews the chemical processes responsible for fractionating deuterium in interstellar molecules. I show that this process is intrinsically a low temperature phenomenon and discuss how the degree of enhancement of the deuterium content of molecules is related to the physical conditions, particularly abundances, in molecular clouds. If significant amounts of abundant species, such as CO, are frozen out on to interstellar dust grains, the resulting enhancement in H₂D⁺ can result in its abundance being greater than that of H ₃ ⁺ at 10K. Transfer of the deuteron from H₂D⁺ can then lead to the efficient formation of multiply deuterated species, such as NHD₂ and ND₃. Fractionation can also occur in grain surface reactions and some simple models are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Cometary Refractory Grains: Interstellar and Nebular Sources

Comets are heterogeneous mixtures of interstellar and nebular materials. The degree of mixing of interstellar sources and nebular sources at different nuclear size scales holds the promise of revealing how cometary particles, cometesimals, and cometary nuclei accreted. We can ascribe cometary materials to interstellar and nebular sources and see how comets probe planet-forming process in our protoplanetary disk. Comets and cometary IDPs contain carbonaceous matter that appears to be either similar to poorly-graphitized (amorphous) carbon, a likely ISM source, or highly labile complex organics, with possible ISM or outer disk heritage. The oxygen fugacity of the solar nebula depends on the dynamical interplay between the inward migration of carbon-rich grains and of icy (water-rich) grains. Inside the water dissociation line, OH^? reacts with carbon to form CO or CO₂, consuming available oxygen and contributing to the canonical low oxygen fugacity. Alternatively, the influx of water vapor and/or oxygen rich dust grains from outer (cooler) disk regions can raise the oxygen fugacity. Low oxygen fugacity of the canonical solar nebula favors the condensation of Mg-rich crystalline silicates and Fe-metal, or the annealing of Fe-Mg amorphous silicates into Mg-rich crystals and Fe-metal via Fe-reduction. High oxygen fugacity nebular conditions favors the condensation of Fe-bearing to Fe-rich crystalline silicates. In the ISM, Fe-Mg amorphous silicates are prevalent, in stark contrast to Mg-rich crystalline silicates that are rare. Hence, cometary Mg-rich crystalline silicates formed in the hot, inner regions of the canonical solar nebula and they are the touchstone for models of the outward radial transport of nebular grains to the comet-forming zone. Stardust samples are dominated by Mg-rich crystalline silicates but also contain abundant Fe-bearing and Fe-rich crystalline silicates that are too large (?0.1 μm) to be annealed Fe-Mg amorphous silicates. By comparison with asteroids, the Stardust Fe-bearing and Fe-rich crystalline silicates suggests partial aqueous alteration in comet nuclei. However, aqueous alteration transforms Fe-rich olivine to phyllosilicates before Mg-rich olivine, and Stardust has Mg-rich and Fe-rich olivine and no phyllosilicates. Hence, we look to a nebular source for the moderately Fe-rich to nearly pure-Fe crystalline silicates. Primitive matrices have Mg-Fe silicates but no phyllosilicates, supporting the idea that Mg-Fe silicates but not phyllosilicates are products of water-rich shocks. Chondrule-formation is a late stage process in our protoplanetary disk. Stardust samples show comet 81P/Wild 2 formed at least as late to incorporate a few chondrules, requiring radial transport of chondrules out to perhaps >20 AU. By similar radial transport mechanisms, collisional fragments of aqueously altered asteroids, in particular achondrites that formed earlier than chondrules, might reach the comet-forming zones. However, Stardust samples do not have phyllosilicates and chondrules are rare. Hence, the nebular refractory grains in comet 81P/Wild 2, as well as other comets, appear to be pre-accretionary with respect to asteroid parent bodies. By discussing nebular pathways for the formation of Fe-rich crystalline silicates, and also phyllosilicates and carbonates, we put forth the view that comets contain both the interstellar ingredients for and the products of nebular transmutation.     

Interstellar Reservoirs of Cometary Matter

We review the evidence for the products of interstellar chemistry in volatile cometary matter. We compare the organic inventory of star-forming cores with that measured in various comets and point out the similarities and differences. The conditions necessary to fractionate interstellar molecules in the heavier isotopes of H, C, O and N are summarised and compared to the measured fractionation ratios in cometary ices. We give a list of future measurements that would shed further light on the putative connection between cometary and interstellar molecules.     

Formation and Processing of Organics in the Early Solar System

Until pristine samples can be returned from cometary nuclei, primitive meteorites represent our best source of information about organic chemistry in the early solar system. However, this material has been affected by secondary processing on asteroidal parent bodies which probably did not affect the material now present in cometary nuclei. Production of meteoritic organic matter apparently involved the following sequence of events: Molecule formation by a variety of reaction pathways in dense interstellar clouds; Condensation of those molecules onto refractory interstellar grains; Irradiation of organic-rich interstellar-grain mantles producing a range of molecular fragments and free radicals; Inclusion of those interstellar grains into the protosolar nebula with probable heating of at least some grain mantles during passage through the shock wave bounding the solar accretion disc; Agglomeration of residual interstellar grains and locally produced nebular condensates into asteroid-sized planetesimals; Heating of planetesimals by decay of extinct radionuclides; Melting of ice to produce liquid water within asteroidal bodies; Reaction of interstellar molecules, fragments and radicals with each other and with the aqueous environment, possibly catalysed by mineral grains; Loss of water and other volatiles to space yielding a partially hydrated lithology containing a complex suite of organic molecules; Heating of some of this organic matter to generate a kerogen-like complex; Mixing of heated and unheated material to yield the meteoritic material now observed. Properties of meteoritic organic matter believed to be consistent with this scenario include: Systematic decrease of abundance with increasing C number in homologous series of characterisable molecules; Complete structural diversity within homologous series; Predominance of branched-chain isomers; Considerable isotopic variability among characterisable molecules and within kerogen-like material; Substantial deuterium enrichment in all organic fractions; Some fractions significantly enriched in nitrogen-15; Modest excesses of L-enantiomers in some racemisation-resistant molecules but no general enantiomeric preference. Despite much speculation about the possible role of Fischer-Tropsch catalytic hydrogenation of CO in production of organic molecules in the solar nebula, no convincing evidence for such material has been found in meteorites. A similarity between some meteoritic organics and those produced by Miller-Urey discharge synthesis may reflect involvement of common intermediates rather than the operation of electric discharges in the early solar system. Meteoritic organic matter constitutes a useful, but not exact, guide to what we shall find with in situ analytical and sample-return missions to cometary nuclei. This revised version was published online in June 2006 with corrections to the Cover Date.     

Cometary Deuterium

Deuterium fractionations in cometary ices provide important clues to the origin and evolution of comets. Mass spectrometers aboard spaceprobe Giotto revealed the first accurate D/H ratios in the water of Comet 1P/Halley. Ground-based observations of HDO in Comets C/1996 B2 (Hyakutake) and C/1995 O1 (Hale-Bopp), the detection of DCN in Comet Hale-Bopp, and upper limits for several other D-bearing molecules complement our limited sample of D/H measurements. On the basis of this data set all Oort cloud comets seem to exhibit a similar ratio in H₂O, enriched by about a factor of two relative to terrestrial water and approximately one order of magnitude relative to the protosolar value. Oort cloud comets, and by inference also classical short-period comets derived from the Kuiper Belt cannot be the only source for the Earth's oceans. The cometary O/C ratio and dynamical reasons make it difficult to defend an early influx of icy planetesimals from the Jupiter zone to the early Earth. D/H measurements of OH groups in phyllosilicate rich meteorites suggest a mixture of cometary water and water adsorbed from the nebula by the rocky grains that formed the bulk of the Earth may be responsible for the terrestrial D/H. The D/H ratio in cometary HCN is 7 times higher than the value in cometary H₂O. Species-dependent D-fractionations occur at low temperatures and low gas densities via ion-molecule or grain-surface reactions and cannot be explained by a pure solar nebula chemistry. It is plausible that cometary volatiles preserved the interstellar D fractionation. The observed D abundances set a lower limit to the formation temperature of (30 ± 10) K. Similar numbers can be derived from the ortho-to-para ratio in cometary water, from the absence of neon in cometary ices and the presence of S₂. Noble gases on Earth and Mars, and the relative abundance of cometary hydrocarbons place the comet formation temperature near 50 K. So far all cometary D/H measurements refer to bulk compositions, and it is conceivable that significant departures from the mean value could occur at the grain-size level. Strong isotope effects as a result of coma chemistry can be excluded for molecules H₂O and HCN. A comparison of the cometary ratio with values found in the atmospheres of the outer planets is consistent with the long-held idea that the gas planets formed around icy cores with a high cometary D/H ratio and subsequently accumulated significant amounts of H₂ from the solar nebula with a low protosolar D/H. This revised version was published online in June 2006 with corrections to the Cover Date.     

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.     

Oxygen Isotope Processes and Transfer Reactions

A unique kinetic isotope effect has been found in the formation process of ozone molecules. Isotope enrichments of about 10% above statistically expected values were first discovered in atmospheric isotopomers ⁴⁹O₃ and ⁵⁰O₃ and later in many other molecular combinations. Most recently the source of this effect was identified through measurement of isotope-specific ozone formation rate coefficients which show a large variability of over 50%. Ozone molecule formation is a complex process since different reaction channels contribute to a specific isotopomer. In addition, fast oxygen isotope exchange reactions determine the abundance of atomic oxygen participating in ozone formation. The isotope enrichments observed are both pressure and temperature-dependent and they decrease at pressures above 100 mbar and toward lower temperatures. Ozone possesses not only one of the most unusual isotope anomalies, it also serves as a mediator by transferring heavy oxygen from the O₂ reservoir to other species. Stratospheric isotope composition of CO₂ has been recently measured with high accuracy and a pronounced isotopic signature was found which shows that ¹⁷O is preferentially transferred from O₃ into CO₂. This revised version was published online in August 2006 with corrections to the Cover Date.     

Origin of Molecular Oxygen in Comets: Current Knowledge and Perspectives

The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) instrument onboard the Rosetta spacecraft has measured molecular oxygen (O₂) in the coma of comet 67P/Churyumov-Gerasimenko (67P/C-G) in surprisingly high abundances. These measurements mark the first unequivocal detection of O₂ in a cometary environment. The large relative abundance of O₂ in 67P/C-G despite its high reactivity and low interstellar abundance poses a puzzle for its origin in comet 67P/C-G, and potentially other comets. Since its detection, there have been a number of hypotheses put forward to explain the production and origin of O₂ in the comet. These hypotheses cover a wide range of possibilities from various in situ production mechanisms to protosolar nebula and primordial origins. Here, we review the O₂ formation mechanisms from the literature, and provide a comprehensive summary of the current state of knowledge of the sources and origin of cometary O₂.