Remote Observations of the Composition of Cometary Volatiles

The volatile species released in the coma are an important clue to the composition of the cometary nucleus ices. Their identification and the measurement of their abundances is possible by remote sensing. Considerable progress has been made recently using radio and infrared spectroscopy, especially with the observations of the two exceptional comets C/1996 B2 (Hyakutake) and C/1995 O1 (Hale-Bopp).) 24 molecules likely to be parent molecules outgassed from the nucleus have now been identified. Significant upper limits exist for many other species, and the presence of unidentified lines suggests that further species are to be identified. In addition, isotopic varieties have been observed for hydrogen, carbon, nitrogen and sulphur. We will review these results with a special emphasis on the reliability of the identifications and of the molecular production rate determinations. A critical point is to assess whether a given species is a genuine parent molecule outgassed from nuclear ices, or is a secondary product coming from grains or from gas-phase photochemistry. Ground-based spectral imaging, such as radio interferometry, may help resolving this problem. This revised version was published online in June 2006 with corrections to the Cover Date.     

From Coma Abundances to Nucleus Composition

A major goal of comet research is to determine conditions in the outer solar nebula based on the chemical composition and structure of comet nuclei. The old view was to use coma abundances directly for the chemical composition of the nucleus. However, since the composition of the coma changes with heliocentric distance, r, the new view is that the nucleus composition msut be determined from analysis of coma mixing ratios as a function of r. Taking advantage of new observing technology and the early detection of the very active Comet Hale-Bopp (C/1995 O1) allows us to determine the coma mixing ratios over a large range of heliocentric distances. In our analysis we assume three sources for the coma gas: (1) the surface of the nucleus (releasing water vapor), (2) the interior of the porous nucleus (releasing many species more volatile than water), and (3) the distributed source (releasing gases from ices and hydrocarbon polycondensates trapped and contained in coma dust). Molecules diffusing inside the nucleus are sublimated by heat transported into the interior. The mixing ratios in the coma are modeled assuming various chemical compositions and structural parameters of the spinning nucleus as it moves in its orbit from large heliocentric distance through perihelion. We have combined several sets of observational data of Comet Hale-Bopp for H₂O (from OH) and CO, covering the spectrum range from radio to UV. Many inconsistencies in the data were uncovered and reported to the observers for a reanalysis. Since post-perihelion data are still sparse, we have combined pre- and post-perihelion data. The resulting mixing ratio of CO relative to H₂O as a function of r is presented with a preliminary analysis that still needs to be expanded further. Our fit to the data indicates that the total CO release rate (from the nucleus and distributed sources) relative to that of H₂O is 30% near perihelion. This revised version was published online in June 2006 with corrections to the Cover Date.     

Morphology–Composition–Isotopes: Recent Results from Observations

This article presents some recent imaging and spectroscopic observations that led to results which are significant for understanding the properties of comet nuclei. The coma morphology and/or composition were investigated for 12 comets belonging to different dynamical classes. The data analysis showed that the coma morphology of three non-periodic comets is not consistent with the general assumption that dynamically new comets still have a relatively uniform nucleus surface and therefore do not exhibit gas and/or dust jets in their coma. The determination of carbon and nitrogen isotopic ratios revealed the same values for all comets investigated at various heliocentric distances. However, the relative abundance of the rare nitrogen isotope ¹⁵N is about twice as high as in the Earth’s atmosphere. Observations of comets at splitting events and during outbursts led to indications for differences between material from the nucleus surface and the interior. The monitoring of the induced outburst of 9P/Temple revealed that under non-steady state conditions the fast disintegration of species is detectable.     

Composition Measurements of a Comet from the Rosetta Orbiter Spacecraft

The European Space Agency (ESA) Rosetta Spacecraft, launched on March 2, 2004 toward Comet 67P/Churyumov-Gerasimenko (C-G), carries a complementary set of instruments on both the orbiter and lander (Philae) portions of the spacecraft, to measure the composition of the Comet C-G. The primary composition measuring instruments on the Orbiter are Alice, COSIMA, ICA, MIRO, OSIRIS, ROSINA and VIRTIS. These instruments collectively are capable of providing compositional information, including temporal and spatial distributions of important atomic, molecular, and ionic species, minerals, and ices in the coma and nucleus. The instruments utilize a variety of techniques and wavelength ranges to accomplish their objectives. This paper provides an overview of composition measurements that will be possible using the suite of orbiter composition measuring instruments. A table is provided that lists important species detectable (depending on abundances) with each instrument.     

Distributed Sources in Comets

The distribution of some molecules and radicals (H₂CO, CO, HNC, CN,?…) in the atmosphere of several comets cannot be explained only by a direct sublimation from the nucleus, or by gas phase processes in the coma. Such molecules are in part the result of a distributed source in the coma, which could be the photo and thermal degradation of dust. We present a review of the degradation processes and discuss possible interpretations of the observations in which the degradation of solid complex organic material in dust particles seems to play a major role. The knowledge of such gas production mechanisms provides important clues on the chemical nature of the refractory organic material contained in comet nuclei.     

Thermal and Chemical Evolution of Comet Nuclei and Kuiper Belt Objects

The structure and composition of comet nuclei are mainly altered during two short phases that are separated by a very long hibernation phase. Early evolution—during and immediately after formation—is the result of heating caused by radioactive decay, the most important source being ²⁶Al. Several studies are reviewed, dealing with evolution throughout this phase, calculated by means of 1-D numerical codes that solve the heat and mass balance equations on a fixed spherically symmetric grid. It is shown that, depending on parameters, the interior may reach temperatures above the melting point of water. The models thus suggest that comets are likely to lose the ices of very volatile species during early evolution; ices of less volatile species are retained in the cold subsurface layer. As the initially amorphous ice is shown to crystallize in the interior, some objects may also lose part of the volatiles trapped in amorphous ice. Generally, the outer layers are far less affected than the inner part, resulting in a stratified composition and altered porosity distribution. The second phase of evolution occurs when comet nuclei are deflected into the inner solar system and is dominated by the effect of solar radiation. Now the outer layers are those mostly affected, undergoing crystallization, loss of volatiles, and significant structural changes. If any part of a comet nucleus should retain its pristine structure and composition, it would be well below the surface and also well above the core.     

Origins of Cometary Materials

In this introductory presentation, material is categorized according to our state of knowledge: What do we know, what do we think we know but don’t know certainly, and what do we not know but often describe it as if it were a well-established fact about comets, their nuclei, their composition, and processes within comets and their nuclei. The material is presented not with the intend to criticize laboratory work simulating condition in comet nuclei, or observers analyzing their observations, nor modelers using data from both these sources to improve our understanding and make predictions. The intent is to provoke discussion and dialog between these groups to avoid overstating the results. What is a Comet? A comet is a diffuse appearing celestial phenomenon moving in an orbit about the Sun. The central body, the nucleus, is composed of ice and dust. It is the source of all cometary activity, including comae and tails. We distinguish between molecular (including atoms and ions) and dust comae. At heliocentric distances of about 1 AU and less, the hydrogen coma typically has dimensions larger than the Sun. The tails are composed of dust, neutral atoms and molecules, and plasma.     

The Coma of Comet 9P/Tempel 1

As comet 9P/Tempel 1 approaches the Sun in 2004–2005, a temporary atmosphere, or “coma,” will form, composed of molecules and dust expelled from the nucleus as its component icy volatiles sublimate. Driven mainly by water ice sublimation at surface temperatures T > 200 K, this coma is a gravitationally unbound atmosphere in free adiabatic expansion. Near the nucleus (≤ 10² km), it is in collisional equilibrium, at larger distances (≥10⁴ km) it is in free molecular flow. Ultimately the coma components are swept into the comet’s plasma and dust tails or simply dissipate into interplanetary space. Clues to the nature of the cometary nucleus are contained in the chemistry and physics of the coma, as well as with its variability with time, orbital position, and heliocentric distance. The DI instrument payload includes CCD cameras with broadband filters covering the optical spectrum, allowing for sensitive measurement of dust in the comet’s coma, and a number of narrowband filters for studying the spatial distribution of several gas species. DI also carries the first near-infrared spectrometer to a comet flyby since the VEGA mission to Halley in 1986. This spectrograph will allow detection of gas emission lines from the coma in unprecedented detail. Here we discuss the current state of understanding of the 9P/Tempel 1 coma, our expectations for the measurements DI will obtain, and the predicted hazards that the coma presents for the spacecraft. An erratum to this article is available at .     

Comets and Chemical Composition

It is commonly believed that comets are made of primordial material. As a consequence, they can reveal more information about the origin of our solar system. To interpret the coma composition measurements of comet Churyumov–Gerasimenko that will be collected by the Rosetta mission, models of the coma chemistry have to be constructed. However, programming the chemistry of a cometary coma is extremely complex due to the large number of species and reactions involved. Moreover, such a program needs to be very flexible as one may want to extend, change, or update the set of species, reactions, and reaction rates. Therefore, we developed software to manage a database of species and reactions and to generate code automatically to compute source/loss balances. This database includes the data from the UMIST database and the ion–molecule reactions collected by V.G. Anicich. To use all these databases together, a lot of practical problems need to be solved, but the result is an enormous source of information about chemical reactions that can be used in chemical models, not only for comets but also for other applications.     

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.     

The interpretations of ultraviolet observations of comets

Summary Ultraviolet observations of comets from above the Earth's atmosphere have provided excellent new results and improved older ground based observations (OH) by an order of magnitude. Satellites are especially suitable because long integration times and observations during extended time intervals are possible.The existing cometary L observations have confirmed the relatively high overall gas production rates on the order of 10³⁰ molecule s^–1. The results strongly support the concept of an icy conglomerate solid cometary nucleus. Additional observations of hydroxyl and oxygen favor water to be one of the most abundant molecules in comets. The observations are in agreement with the predominent role of water in the evaporation process of the nuclear ices but are not proof in themselves.Water did not outnumber other consitutents by orders of magnitude in comets Bennett and Kohoutek. At least in these comets, carbon-containing molecules were possibly as numerous as water. Determination of the carbon scale length is necessary for a more quantitative statement.A hydrogen velocity of 7–9 km s^–1 was observed in comet Bennett as well as in comet Kohoutek for a variety of heliocentric distances and varying production rates. Determinations of the outflow velocity from L isophotes agree with line profile observations of L and H. Hydroxyl may constitute the main source for the hydrogen atoms with v _H - 8 km s^–1. The decay process, however, leading to this particular velocity is not yet known. Possibly a large portion of the OH radicals do not decay into hydrogen atoms or at least not into slow ones. If the high velocity component of 20 km s^–1 or more comprises a larger amount (up to 50%), most of the quoted hydrogen production rates must be revised upward.The intrinsic cometary brightness is only a very crude indicator of a comet's actual gas production rate as shown by comparison of comets Bennett and TSK. Comets can be successfully used as (extra ecliptic) space probes to measure interplanetary quantities, e.g., the curvature of the extended hydrogen clouds can be used for the absolute determination of the solar emission independent of instrumental calibration. Generally time dependent hydrogen density models must be used for the interpretation. The strength of the ultraviolet L emission favors its measurement as a standard procedure for the observation of comets (possibly together with OH (3090 Å)). These observations provide the most accurate results on the total cometary gas production rate and its variation with heliocentric distance.Dedicated to Professor L. Biermann in recognition of his inspiring guidance.On leave of absence from Max-Planck-Institut für Physik und Astrophysik, Munich.     

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.     

The Deep Impact Earth-Based Campaign

Prior to the selection of the comet 9P/Tempel 1 as the Deep Impact mission target, the comet was not well observed. From 1999 through the present there has been an intensive world-wide observing campaign designed to obtain mission critical information about the target nucleus, including the nucleus size, albedo, rotation rate, rotation state, phase function, and the development of the dust and gas coma. The specific observing schemes used to obtain this information and the resources needed are presented here. The Deep Impact mission is unique in that part of the mission observations will rely on an Earth-based (ground and orbital) suite of complementary observations of the comet just prior to impact and in the weeks following. While the impact should result in new cometary activity, the actual physical outcome is uncertain, and the Earth-based observations must allow for a wide range of post-impact phenomena. A world-wide coordinated effort for these observations is described.     

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.     

Deep Impact: The Anticipated Flight Data

A comprehensive observational sequence using the Deep Impact (DI) spacecraft instruments (consisting of cameras with two different focal lengths and an infrared spectrometer) will yield data that will permit characterization of the nucleus and coma of comet Tempel 1, both before and after impact by the DI Impactor. Within the constraints of the mission system, the planned data return has been optimized. A subset of the most valuable data is planned for return in near-real time to ensure that the DI mission success criteria will be met even if the spacecraft should not survive the comet’s closest approach. The remaining prime science data will be played back during the first day after the closest approach. The flight data set will include approach observations spanning the 60 days prior to encounter, pre-impact data to characterize the comet at high resolution just prior to impact, photos from the Impactor as it plunges toward the nucleus surface (including resolutions exceeding 1 m), sub-second time sampling of the impact event itself from the Flyby spacecraft, monitoring of the crater formation process and ejecta outflow for over 10 min after impact, observations of the interior of the fully formed crater at spatial resolutions down to a few meters, and high-phase lookback observations of the nucleus and coma for 60 h after closest approach. An inflight calibration data set to accurately characterize the instruments’ performance is also planned. A ground data processing pipeline is under development at Cornell University that will efficiently convert the raw flight data files into calibrated images and spectral maps as well as produce validated archival data sets for delivery to NASA’s Planetary Data System within 6 months after the Earth receipt for use by researchers world-wide.     

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.     

Expectations for Infrared Spectroscopy of 9P/Tempel 1 from Deep Impact

The science payload on the Deep Impact mission includes a 1.05–4.8 μm infrared spectrometer with a spectral resolution ranging from R∼200–900. The Deep Impact IR spectrometer was designed to optimize, within engineering and cost constraints, observations of the dust, gas, and nucleus of 9P/Tempel 1. The wavelength range includes absorption and emission features from ices, silicates, organics, and many gases that are known to be, or anticipated to be, present on comets. The expected data will provide measurements at previously unseen spatial resolution before, during, and after our cratering experiment at the comet 9P/Tempel 1. This article explores the unique aspects of the Deep Impact IR spectrometer experiment, presents a range of expectations for spectral data of 9P/Tempel 1, and summarizes the specific science objectives at each phase of the mission.     

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.