The composition of cometary ices.

The chemical composition of cometary ices provides clues for the conditions of formation and evolution of the early Solar System. A large number of molecules have been identified in cometary atmospheres, from both ground-based observations and space, including in situ investigations. This includes large organic molecules, which are also observed in star-forming regions. This paper presents a review of molecular abundances measured in cometary atmospheres from remote sensing observations with ground-based and space-based telescopes. The diversity of composition observed in comet populations is presented and discussed.This article is part of the themed issue 'Cometary science after Rosetta'.

Seasonal exposure of carbon dioxide ice on the nucleus of comet 67P/Churyumov-Gerasimenko.

Carbon dioxide (CO2) is one of the most abundant species in cometary nuclei, but because of its high volatility, CO2 ice is generally only found beneath the surface. We report the infrared spectroscopic identification of a CO2 ice-rich surface area located in the Anhur region of comet 67P/Churyumov-Gerasimenko. Spectral modeling shows that about 0.1% of the 80- by 60-meter area is CO2 ice. This exposed ice was observed a short time after the comet exited local winter; following the increased illumination, the CO2 ice completely disappeared over about 3 weeks. We estimate the mass of the sublimated CO2 ice and the depth of the eroded surface layer. We interpret the presence of CO2 ice as the result of the extreme seasonal changes induced by the rotation and orbit of the comet.

Exposed water ice on the nucleus of comet 67P/Churyumov-Gerasimenko.

Although water vapour is the main species observed in the coma of comet 67P/Churyumov-Gerasimenko and water is the major constituent of cometary nuclei, limited evidence for exposed water-ice regions on the surface of the nucleus has been found so far. The absence of large regions of exposed water ice seems a common finding on the surfaces of many of the comets observed so far. The nucleus of 67P/Churyumov-Gerasimenko appears to be fairly uniformly coated with dark, dehydrated, refractory and organic-rich material. Here we report the identification at infrared wavelengths of water ice on two debris falls in the Imhotep region of the nucleus. The ice has been exposed on the walls of elevated structures and at the base of the walls. A quantitative derivation of the abundance of ice in these regions indicates the presence of millimetre-sized pure water-ice grains, considerably larger than in all previous observations. Although micrometre-sized water-ice grains are the usual result of vapour recondensation in ice-free layers, the occurrence of millimetre-sized grains of pure ice as observed in the Imhotep debris falls is best explained by grain growth by vapour diffusion in ice-rich layers, or by sintering. As a consequence of these processes, the nucleus can develop an extended and complex coating in which the outer dehydrated crust is superimposed on layers enriched in water ice. The stratigraphy observed on 67P/Churyumov-Gerasimenko is therefore the result of evolutionary processes affecting the uppermost metres of the nucleus and does not necessarily require a global layering to have occurred at the time of the comet's formation.

The diurnal cycle of water ice on comet 67P/Churyumov-Gerasimenko.

Observations of cometary nuclei have revealed a very limited amount of surface water ice, which is insufficient to explain the observed water outgassing. This was clearly demonstrated on comet 9P/Tempel 1, where the dust jets (driven by volatiles) were only partially correlated with the exposed ice regions. The observations of 67P/Churyumov-Gerasimenko have revealed that activity has a diurnal variation in intensity arising from changing insolation conditions. It was previously concluded that water vapour was generated in ice-rich subsurface layers with a transport mechanism linked to solar illumination, but that has not hitherto been observed. Periodic condensations of water vapour very close to, or on, the surface were suggested to explain short-lived outbursts seen near sunrise on comet 9P/Tempel 1. Here we report observations of water ice on the surface of comet 67P/Churyumov-Gerasimenko, appearing and disappearing in a cyclic pattern that follows local illumination conditions, providing a source of localized activity. This water cycle appears to be an important process in the evolution of the comet, leading to cyclical modification of the relative abundance of water ice on its surface.

Cometary science. The organic-rich surface of comet 67P/Churyumov-Gerasimenko as seen by VIRTIS/Rosetta.

The VIRTIS (Visible, Infrared and Thermal Imaging Spectrometer) instrument on board the Rosetta spacecraft has provided evidence of carbon-bearing compounds on the nucleus of the comet 67P/Churyumov-Gerasimenko. The very low reflectance of the nucleus (normal albedo of 0.060 ± 0.003 at 0.55 micrometers), the spectral slopes in visible and infrared ranges (5 to 25 and 1.5 to 5% kÅ(-1)), and the broad absorption feature in the 2.9-to-3.6-micrometer range present across the entire illuminated surface are compatible with opaque minerals associated with nonvolatile organic macromolecular materials: a complex mixture of various types of carbon-hydrogen and/or oxygen-hydrogen chemical groups, with little contribution of nitrogen-hydrogen groups. In active areas, the changes in spectral slope and absorption feature width may suggest small amounts of water-ice. However, no ice-rich patches are observed, indicating a generally dehydrated nature for the surface currently illuminated by the Sun.

The surface composition and temperature of asteroid 21 Lutetia as observed by Rosetta/VIRTIS.

The Visible, InfraRed, and Thermal Imaging Spectrometer (VIRTIS) on Rosetta obtained hyperspectral images, spectral reflectance maps, and temperature maps of the asteroid 21 Lutetia. No absorption features, of either silicates or hydrated minerals, have been detected across the observed area in the spectral range from 0.4 to 3.5 micrometers. The surface temperature reaches a maximum value of 245 kelvin and correlates well with topographic features. The thermal inertia is in the range from 20 to 30 joules meter(-2) kelvin(-1) second(-0.5), comparable to a lunarlike powdery regolith. Spectral signatures of surface alteration, resulting from space weathering, seem to be missing. Lutetia is likely a remnant of the primordial planetesimal population, unaltered by differentiation processes and composed of chondritic materials of enstatitic or carbonaceous origin, dominated by iron-poor minerals that have not suffered aqueous alteration.

Compositional homogeneity in the fragmented comet 73P/Schwassmann-Wachmann 3.

The remarkable compositional diversity of volatile ices within comets can plausibly be attributed to several factors, including differences in the chemical, thermal and radiation environments in comet-forming regions, chemical evolution during their long storage in reservoirs far from the Sun, and thermal processing by the Sun after removal from these reservoirs. To determine the relevance of these factors, measurements of the chemistry as a function of depth in cometary nuclei are critical. Fragmenting comets expose formerly buried material, but observational constraints have in the past limited the ability to assess the importance of formative conditions and the effects of evolutionary processes on measured composition. Here we report the chemical composition of two distinct fragments of 73P/Schwassmann-Wachmann 3. The fragments are remarkably similar in composition, in marked contrast to the chemical diversity within the overall comet population and contrary to the expectation that short-period comets should show strong compositional variation with depth in the nucleus owing to evolutionary processing from numerous close passages to the Sun. Comet 73P/Schwassmann-Wachmann 3 is also depleted in the most volatile ices compared to other comets, suggesting that the depleted carbon-chain chemistry seen in some comets from the Kuiper belt reservoir is primordial and not evolutionary.

Deep Impact: observations from a worldwide Earth-based campaign.

On 4 July 2005, many observatories around the world and in space observed the collision of Deep Impact with comet 9P/Tempel 1 or its aftermath. This was an unprecedented coordinated observational campaign. These data show that (i) there was new material after impact that was compositionally different from that seen before impact; (ii) the ratio of dust mass to gas mass in the ejecta was much larger than before impact; (iii) the new activity did not last more than a few days, and by 9 July the comet's behavior was indistinguishable from its pre-impact behavior; and (iv) there were interesting transient phenomena that may be correlated with cratering physics.

Outgassing behavior and composition of comet C/1999 S4 (LINEAR) during its disruption.

The gas activity of comet C/1999 S4 (LINEAR) was monitored at radio wavelengths during its disruption. A runaway fragmentation of the nucleus may have begun around 18 July 2000 and proceeded until 23 July. The mass in small icy debris (

A determination of the HDO/H2O ratio in comet C/1995 O1 (Hale-Bopp).

Deuterated water (HDO) was detected in comet C/1995 O1 (Hale-Bopp) with the use of the James Clerk Maxwell Telescope on Mauna Kea, Hawaii. The inferred D/H ratio in Hale-Bopp's water is (3.3 +/- 0.8) x 10(-4). This result is consistent with in situ measurements of comet P/Halley and the value found in C/1996 B2 (Hyakutake). This D/H ratio, higher than that in terrestrial water and more than 10 times the value for protosolar H2, implies that comets cannot be the only source for the oceans on Earth.

The spectrum of comet Hale-Bopp (C/1995 O1) observed with the Infrared Space Observatory at 2.9 astronomical units from the sun.

Comet Hale-Bopp (C/1995 O1) was observed at wavelengths from 2.4 to 195 micrometers with the Infrared Space Observatory when the comet was about 2.9 astronomical units (AU) from the sun. The main observed volatiles that sublimated from the nucleus ices were water, carbon monoxide, and carbon dioxide in a ratio (by number) of 10:6:2. These species are also the main observed constituents of ices in dense interstellar molecular clouds; this observation strengthens the links between cometary and interstellar material. Several broad emission features observed in the 7- to 45-micrometer region suggest the presence of silicates, particularly magnesium-rich crystalline olivine. These features are similar to those observed in the dust envelopes of Vega-type stars.

Evolution of the outgassing of comet Hale-Bopp (C/1995 O1) from radio observations.

Spectra obtained from ground-based radio telescopes show the progressive release of CO, CH3OH, HCN, H2O (from OH), H2S, CS, H2CO, CH3CN, and HNC as comet Hale-Bopp (C/1995 01) approached the sun from 6.9 to 1.4 astronomical units (AU). The more volatile species were relatively more abundant in the coma far from the sun, but there was no direct correlation between overabundance and volatility. Evidence for H2O sublimation from icy grains was seen beyond 3.5 AU from the sun. The change from a CO-driven coma to an H2O-driven coma occurred at about 3 AU. The gas outflow velocity and temperature increased as Hale-Bopp approached the sun.

Spectroscopic evidence for interstellar ices in comet Hyakutake.

Volatile compounds in comets are the most pristine materials surviving from the time of formation of the Solar System, and thus potentially provide information about conditions that prevailed in the primitive solar nebula. Moreover, comets may have supplied a substantial fraction of the volatiles on the terrestrial planets, perhaps including organic compounds that played a role in the origin of life on Earth. Here we report the detection of hydrogen isocyanide (HNC) in comet Hyakutake. The abundance of HNC relative to hydrogen cyanide (HCN) is very similar to that observed in quiescent interstellar molecular clouds, and quite different from the equilibrium ratio expected in the outermost solar nebula, where comets are thought to form. Such a departure from equilibrium has long been considered a hallmark of gas-phase chemical processing in the interstellar medium, suggesting that interstellar gases have been incorporated into the comet's nucleus, perhaps as ices frozen onto interstellar grains. If this interpretation is correct, our results should provide constraints on the temperature of the solar nebula, and the subsequent chemical processes that occurred in the region where comets formed.

Detection of acetylene in the infrared spectrum of comet Hyakutake.

Comets are rich in volatile materials, of which roughly 80% (by number) are water molecules. Considerable progress is being made in identifying the other volatile species, the abundances of which should enable us to determine whether comets formed primarily from ice-covered interstellar grains, or from material that was chemically processed in the early solar nebula. Here we report the detection of acetylene (C2H2) in the infrared spectrum of comet C/1996 B2 (Hyakutake). The estimated abundance is 0.3-0.9%, relative to water, which is comparable to the predicted solid-phase abundance in cold interstellar clouds. This suggests that the volatiles in comet Hyakotake may have come from ice-covered interstellar grains, rather than material processed in the accretion disk out of which the Solar System formed.

Substantial outgassing of CO from comet Hale-Bopp at large heliocentric distance.

When comet C/1995 O1 (Hale-Boop) was discovered, at a distance of seven astronomical units from the sun, it was more than one hundred times brighter than comet Halley at the same distance. A comet's brightness is derived from the reflection of sunlight from dust grains driven away from the nucleus by the sublimation of volatile ices. Near the sun, sublimation of water ice (a main constituent of comet nuclei) is the source of cometary activity; but at its current heliocentric distance, Hale-Boop is too cold for this process to operate. Other comets have shown activity at large distances, and in the case of comet Schwassmann-Wachmann 1, carbon monoxide has been detected in quantities sufficient to generate its observed coma. Here we report the detection of CO emission from Hale-Boop, at levels indicating a very large rate of outgassing. Several other volatile species were searched for, but not detected. Sublimation of CO therefore appears to be responsible for the present activity of this comet, and we anticipate that future observations will reveal the onset of sublimation of other volatile species as the comet continues its present journey towards the sun.

Chemical and thermal response of Jupiter's atmosphere following the impact of comet Shoemaker-Levy 9.

In July 1994, the collisions of the fragments of comet Shoemaker-Levy 9 with Jupiter resulted in dramatic changes in the planet's atmosphere. Observations of the events suggest that the composition and thermal properties of the atmosphere were considerably modified at the impact sites, with the changes persisting for times lasting from minutes to weeks (see, for example, refs 1-4). Here we report observations of the impact sites at millimetre wave-lengths, which reveal strong emission lines associated with carbon monoxide, carbonyl sulphide and carbon monosulphide. The abundance of carbon monoxide in the jovian atmosphere is normally very low; carbonyl sulphide and carbon monosulphide, on the other hand, have not hitherto been detected. We find that the largest fragments (G and K) each produced approximately 10(14) g of carbon monoxide, 3 x 10(12) g of carbonyl sulphide and 3 x 10(11) g of carbon monosulphide, most probably by shock-induced chemical reactions. Our observations also place firm constraints on the thermal response of Jupiter's stratosphere to the impacts.

The 2.5-12 micrometers spectrum of comet Halley from the IKS-VEGA experiment.

The infrared instrument IKS flown on board the VEGA space probes was designed for the detection of emission bands of parent molecules, and for a measurement of the size and temperature of the thermal emitting nuclear region. The instrument had three channels with cooled detectors: an "imaging channel" designed to modulate the signal of the nucleus and two spectroscopic channels operating at 2.5-5 and 6-12 micrometers, respectively, equipped with circular variable filters of resolving power approximately 50. This paper presents and discusses the results from the spectral channels. On VEGA 1, usable spectra were obtained at distances D from the comet nucleus ranging from 250,000 to 40,000 km corresponding to fields of view 4000 and 700 km in diameter, respectively. The important internal background signal caused by the instrument itself, which could not be cooled, had to be eliminated. Since no sky chopping was performed, we obtain difference spectra between the current spectrum and a reference spectrum with little or no cometary signal taken at the beginning of the observing sequence (D approximately 200,000 km). Final discrimination between cometary signal and instrumental background is achieved using their different time evolution, since the instrumental background is proportional to the slow temperature drift of the instrument, and the cometary signal due to parent molecules or dust grains is expected to vary in first order as D-1. The 2.5-5 micrometers IKS spectra definitely show strong narrow signals at 2.7 and 4.25 micrometers, attributed to the nu 3 vibrational bands of H2O and CO2, respectively, and a broader signal in the region 3.2-3.5 micrometers, which may be attributed to CH-bearing molecules. All these signals present the expected D-1 intensity variation. Weaker emission features at 3.6 and 4.7 micrometers could correspond to the nu 1 and nu 5 bands of H2CO and the (1 - 0) band of CO, respectively. Molecular production rates are derived from the observed emissions, assuming that they are due to resonance fluorescence excited by the Sun's infrared radiation. For the strong bands of H2O and CO2, the rovibrational lines are optically thick, and radiative transfer is taken into account. We derive production rates, at the moment of the VEGA 1 flyby, of approximately 10(30) sec-1 for H2O, approximately 2.7 x 10(28) sec-1 for CO2, approximately 5 x 10(28) sec-1 for CO, and 4 x 10(28) sec-1 for H2CO, if attributions to CO and H2CO are correct. The production rate of carbon atoms in CH-bearing molecules is approximately 9 x 10(29) sec-1 assuming fluorescence of molecules in the gas phase, but could be much less if the 3.2-3.5 micrometers emission is attributed to C-H stretch in polycyclic aromatic hydrocarbons or small organic grains. In addition, marginal features are present at 4.85 and 4.45 micrometers, tentatively attributed to OCS and molecules with the CN group, respectively. Broad absorption at 2.8-3.0 micrometers, as well as a narrow emission at 3.15 micrometers, which follow well the D-1 intensity variation, might be due to water ice. Emission at 2.8 micrometers is also possibly present, and might be due to OH created in vibrationally excited states after water photodissociation. The 6-12 micrometers spectrum does not show any molecular emission, nor emission in the 7.5-micrometers region. The spectrum is dominated by silicate emission showing a double structure with maxima at 9.0 and 11.2 micrometers, which suggests the presence of olivine.