Isotopic analysis of cometary organic matter

Carbon isotope ratios have been measured for CN in the coma of comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of ¹³C/¹²C values in those particles is quite uncertain. The D/H ratio in H₂O in the Halley coma resembles that in Titan/Uranus. The next decade should substantially improve our understanding of the distribution of C, H, N, and O isotopes in cometary organics. The isotopic composition of meteoritic organic matter is better understood and can serve as a useful analog for the cometary case.     

Rocky Cometary Particulates: Their Elemental,Isotopic and Mineralogical Ingredients

The determination of the chemical composition of solid cometary dust particles was one of the prime objectives of the three missions to Comet Halley in 1986. The dust analysis was performed by time-of-flight mass-spectrometry. Within the experimental uncertainty the mean abundances of the rock-forming elements in cometary dust particles are comparable to their abundances in CI-chondrites and in the solar photosphere, i.e. they are cosmic. H, C, and N, on the other hand, in cometary dust are significantly more abundant than in CI-chondrites, approach solar abundances, are to some extent related to O, and reside in an omnipresent refractory organic component dubbed CHON. Element variations between individual dust grains are characterized by correlations of Mg, Si, and O, and to a lesser extent of Fe and S. From particle-to-particle variations of the rock forming elements information on the mineralogy of cometary dust can be obtained. Cluster analysis revealed certain groups that partly match the classifications of stratospheric interplanetary dust particles. About half of Halley's analyzed particles are characterized by anhydrous Fe-poor Mg-silicates, Fe-sulfides, and rarely Fe metal. The Fe-poor Mg-silicates link Halley's dust to that of Hale-Bopp as shown by recent IR observations. No significant deviation from normal of the isotopic composition of the elements is unequivocally present with the notable exception carbon: ¹²C-rich grains with ¹²C/¹³C-ratios up to ≈ 5,000 link cometary dust to presolar circumstellar grains identified in certain chondrites. This revised version was published online in June 2006 with corrections to the Cover Date.     

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.     

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.     

Martian Volatiles: Isotopic Composition, Origin, and Evolution

Information about the composition of volatiles in the Martian atmosphere and interior derives from Viking spacecraft and ground-based measurements, and especially from measurements of volatiles trapped in Martian meteorites, which contain several distinct components. One volatile component, found in impact glass in some shergottites, gives the most precise measurement to date of the composition of Martian atmospheric Ar, Kr, and Xe, and also contains significant amounts of atmospheric nitrogen showing elevated ¹⁵N/¹⁴N. Compared to Viking analyses, the ³⁶Ar/¹³²Xe and ⁸⁴Kr/¹³²Xe elemental ratios are larger in shergottites, the ¹²⁹Xe/¹³²Xe ratio is similar, and the ⁴⁰Ar/³⁶Ar and ³⁶Ar/³⁸Ar ratios are smaller. The isotopic composition of atmospheric Kr is very similar to solar Kr, whereas the isotopes of atmospheric Xe have been strongly mass fractionated in favor of heavier isotopes. The nakhlites and ALH84001 contain an atmospheric component elementally fractionated relative to the recent atmospheric component observed in shergottites. Several Martian meteorites also contain one or more Martian interior components that do not show the mass fractionation observed in atmospheric noble gases and nitrogen. The D/H ratio in the atmosphere is strongly mass fractionated, but meteorites contain a distinct Martian interior hydrogen component. The isotopic composition of Martian atmospheric carbon and oxygen have not been precisely measured, but these elements in meteorites appear to show much less variation in isotopic composition, presumably in part because of buffering of the atmospheric component by larger condensed reservoirs. However, differences in the oxygen isotopic composition between meteorite silicate minerals (on the one hand) and water and carbonates indicate a lack of recycling of these volatiles through the interior. Many models have been presented to explain the observed isotopic fractionation in Martian atmospheric N, H, and noble gases in terms of partial loss of the planetary atmosphere, either very early in Martian history, or over extended geological time. The number of variables in these models is large, and we cannot be certain of their detailed applicability. Evolutionary data based on the radiogenic isotopes (i.e., ⁴⁰Ar/³⁶Ar, ¹²⁹Xe/¹³²Xe, and ¹³⁶Xe/¹³²Xe ratios) are potentially important, but meteorite data do not yet permit their use in detailed chronologies. The sources of Mars' original volatiles are not well defined. Some Martian components require a solar-like isotopic composition, whereas volatiles other than the noble gases (C, N, and H₂O) may have been largely contributed by a carbonaceous (or cometary) veneer late in planet formation. Also, carbonaceous material may have been the source of moderate amounts of water early in Martian history.     

The Genesis Solar Wind Concentrator

The primary goal of the Genesis Mission is to collect solar wind ions and, from their analysis, establish key isotopic ratios that will help constrain models of solar nebula formation and evolution. The ratios of primary interest include ¹⁷O/¹⁶O and ¹⁸O/¹⁶O to ±0.1%, ¹⁵N/¹⁴N to ±1%, and the Li, Be, and B elemental and isotopic abundances. The required accuracies in N and O ratios cannot be achieved without concentrating the solar wind and implanting it into low-background target materials that are returned to Earth for analysis. The Genesis Concentrator is designed to concentrate the heavy ion flux from the solar wind by an average factor of at least 20 and implant it into a target of ultra-pure, well-characterized materials. High-transparency grids held at high voltages are used near the aperture to reject >90% of the protons, avoiding damage to the target. Another set of grids and applied voltages are used to accelerate and focus the remaining ions to implant into the target. The design uses an energy-independent parabolic ion mirror to focus ions onto a 6.2 cm diameter target of materials selected to contain levels of O and other elements of interest established and documented to be below 10% of the levels expected from the concentrated solar wind. To optimize the concentration of the ions, voltages are constantly adjusted based on real-time solar wind speed and temperature measurements from the Genesis ion monitor. Construction of the Concentrator required new developments in ion optics; materials; and instrument testing and handling. This revised version was published online in August 2006 with corrections to the Cover Date.     

Isotopic Composition of the Solar Wind Inferred from In-Situ Spacecraft Measurements

The Sun is the largest reservoir of matter in the solar system, which formed 4.6 Gyr ago from the protosolar nebula. Data from space missions and theoretical models indicate that the solar wind carries a nearly unfractionated sample of heavy isotopes at energies of about 1 keV/amu from the Sun into interplanetary space. In anticipation of results from the Genesis mission’s solar-wind implanted samples, we revisit solar wind isotopic abundance data from the high-resolution CELIAS/MTOF spectrometer on board SOHO. In particular, we evaluate the isotopic abundance ratios ¹⁵N/¹⁴N, ¹⁷O/¹⁶O, and ¹⁸O/¹⁶O in the solar wind, which are reference values for isotopic fractionation processes during the formation of terrestrial planets as well as for the Galactic chemical evolution. We also give isotopic abundance ratios for He, Ne, Ar, Mg, Si, Ca, and Fe measured in situ in the solar wind.     

The Composition of the Solar Wind in Polar Coronal Holes

The solar wind charge state and elemental compositions have been measured with the Solar Wind Ion Composition Spectrometers (SWICS) on Ulysses and ACE for a combined period of about 25 years. This most extensive data set includes all varieties of solar wind flows and extends over more than one solar cycle. With SWICS the abundances of all charge states of He, C, N, O, Ne, Mg, Si, S, Ar and Fe can be reliably determined (when averaged over sufficiently long time periods) under any solar wind flow conditions. Here we report on results of our detailed analysis of the elemental composition and ionization states of the most unbiased solar wind from the polar coronal holes during solar minimum in 1994–1996, which includes new values for the abundance S, Ca and Ar and a more accurate determination of the ²⁰Ne abundance. We find that in the solar minimum polar coronal hole solar wind the average freezing-in temperature is ∼1.1×10⁶ K, increasing slightly with the mass of the ion. Using an extrapolation method we derive photospheric abundances from solar wind composition measurements. We suggest that our solar-wind-derived values should be used for the photospheric ratios of Ne/Fe=1.26±0.28 and Ar/Fe=0.030±0.007.     

On the Organic Refractory Component of Cometary Dust

Cometary nuclei consist of ices intermixed with dust grains and are thought to be the least modified solar system bodies remaining from the time of planetary formation. Flyby missions to Comet P/Halley in 1986 showed that cometary dust is extremely rich in organics (∼50% by mass). However, this proportion appears to be variable among different comets. In comparison with the CI-chondritic abundances, the volatile elements H, C, and N are enriched in cometary dust indicating that cometary solid material is more primitive than CI-chondrites. Relative to dust in dense molecular clouds, bulk cometary dust preserves the abundances of C and N, but exhibits depletions in O and H. In most cases, the carbonaceous component of cometary particles can be characterized as a multi-component mixture of carbon phases and organic compounds. Cluster analysis identified a few basic types of compounds, such as elemental carbon, hydrocarbons, polymers of carbon suboxide and of cyanopolyynes. In smaller amounts, polymers of formaldehyde, of hydrogen cyanide and various unsaturated nitriles also are present. These compositionally simple types, probably, are essential "building blocks", which in various combinations give rise to the variety of involatile cometary organics. This revised version was published online in June 2006 with corrections to the Cover Date.     

Solar and Solar-Wind Composition Results from the Genesis Mission

The Genesis mission returned samples of solar wind to Earth in September 2004 for ground-based analyses of solar-wind composition, particularly for isotope ratios. Substrates, consisting mostly of high-purity semiconductor materials, were exposed to the solar wind at L1 from December 2001 to April 2004. In addition to a bulk sample of the solar wind, separate samples of coronal hole (CH), interstream (IS), and coronal mass ejection material were obtained. Although many substrates were broken upon landing due to the failure to deploy the parachute, a number of results have been obtained, and most of the primary science objectives will likely be met. These objectives include He, Ne, Ar, Kr, and Xe isotope ratios in the bulk solar wind and in different solar-wind regimes, and ¹⁵N/¹⁴N and ¹⁸O/¹⁷O/¹⁶O to high precision. The greatest successes to date have been with the noble gases. Light noble gases from bulk solar wind and separate solar-wind regime samples have now been analyzed. Helium results show clear evidence of isotopic fractionation between CH and IS samples, consistent with simplistic Coulomb drag theory predictions of fractionation between the photosphere and different solar-wind regimes, though fractionation by wave heating is also a possible explanation. Neon results from closed system stepped etching of bulk metallic glass have revealed the nature of isotopic fractionation as a function of depth, which in lunar samples have for years deceptively suggested the presence of an additional, energetic component in solar wind trapped in lunar grains and meteorites. Isotope ratios of the heavy noble gases, nitrogen, and oxygen are in the process of being measured.     

Isotopes in comets: Implications from Cr in carbonaceous chondrites

According to their chemical composition, rich in volatile compounds, comets are thought to be primitive materials. They may provide prime samples for the study of nucleosynthetic components of the solar system and of the processes occurring during the formation of the outer planets. Their origin is largely a matter of conjecture. Chromium isotopic measurements in carbonaceous chondrites illustrate how the non-volatile part of cometary material can be investigated both for isotopic heterogeneity and for the extinct nuclide ⁵³Mn. Questions like the possible presence of ²⁶Al as a heat source can also be addressed by these measurements.     

The isotopic composition of anomalous cosmic rays from sampex

Measurements of the anomalous cosmic ray (ACR) isotopic composition have been made in three regions of the magnetosphere accessible from the polar Earth orbit of SAMPEX, including the interplanetary medium at high latitudes and geomagnetically trapped ACRs. At those latitudes where ACRs can penetrate the Earth's magnetic field while fully stripped galactic cosmic rays (GCRs) of similar energies are excluded, a pure ACR sample is observed to have the following composition: ¹⁵N/N < 0.023, ¹⁸O/¹⁶O < 0.0034, and ²²Ne/²⁰Ne = 0.077(+0.085, –0.023). We compare our values with those found by previous investigators and with those measured in other samples of solar and galactic material. In particular, a comparison of ²²Ne/²⁰Ne measurements from various sources implies that GCRs are not simply an accelerated sample of the local interstellar medium.     

Oxygen and carbon abundances for the WO stars

We present relative carbon and oxygen abundances derived via an optically thin recombination line analysis for five WO stars, and compare the derived abundances to recent evolutionary models. New recombination coefficients for O⁴⁺, O⁵⁺ and O⁶⁺ ions have allowed total oxygen abundances to be derived. The final C/He values range between 0.4 and 0.8 by number, consistent with C/He ratios previously derived for WC stars. O/He values range between 0.1–0.4, with C/O ratios between 2.1–4.8.A comparison of the derived abundances with the evolutionary models of Maeder (1990) and Schaller et al. (1992) shows promising agreement. We find reasonably tight agreement between the abundances derived for the WO stars. The degree of enhancement for the oxygen abundances in regions of low metallicity predicted by Maeder (1990) is not corroborated by our results.Additionally we present a revised, quantified classification scheme for WO subtypes. We extend the class to lower excitation, WO5, and place MS 4 (=WR 30a) in this class. Equivalent widths of the strongest lines of MS 4 are also presented. Finally, we present new observations of DR 1, a WO3 star located in the dwarf irregular galaxy IC 1613.     

Composition of anomalous cosmic rays and implications for the heliosphere

We use energy spectra of anomalous cosmic rays (ACRs) measured with the Cosmic Ray instrument on the Voyager 1 and 2 spacecraft during the period 1994/157-313 to determine several parameters of interest to heliospheric studies. We estimate that the strength of the solar wind termination shock is 2.42 (–0.08, +0.04). We determine the composition of ACRs by estimating their differential energy spectra at the shock and find the following abundance ratios: H/He = 5.6 (–0.5, ⁺0.6), C/He = 0.00048 ± 0.00011, N/He = 0.011 ± 0.001, O/He = 0.075 ± 0.006, and Ne/He = 0.0050 ± 0.0004. We correlate our observations with those of pickup ions to deduce that the long-term ionization rate of neutral nitrogen at 1 AU is 8.3 × 10^–7 s^–1 and that the charge-exchange cross section for neutral N and solar wind protons is 1.0 × 10^–15 cm² at 1.1 keV. We estimate that the neutral C/He ratio in the outer heliosphere is 1.8(–0.7, +0.9) × 10^–5. We also find that heavy ions are preferentially injected into the acceleration process at the termination shock.     

Composition of Interstellar Neutrals and the Origin of Anomalous Cosmic Rays

Knowledge of the elemental composition of the interstellar gas is of fundamental importance for understanding galactic chemical evolution. In addition to spectroscopic determinations of certain element abundance ratios, measurements of the composition of interstellar pickup ions and Anomalous Cosmic Rays (ACRs) have provided the principal means to obtain this critical information. Recent advances in our understanding of particle acceleration processes in the heliosphere and measurements by the Voyagers of the energy spectra and composition of energetic particles in the heliosheath provide us with another means of determining the abundance of the neutral components of the local interstellar gas. Here we compare the composition at the termination shock of six elements obtained from measurements of (a) pickup ions at ～5 AU, (b) ACRs in the heliosphere at ～70 AU, and (c) energetic particles as well as (d) ACRs in the heliosheath at ～100 AU. We find consistency among these four sets of derived neutral abundances. The average interstellar neutral densities at the termination shock for H, N, O, Ne and Ar are found to be 0.055±0.021 cm^?3, (1.44±0.45)×10^?5 cm^?3, (6.46±1.89)×10^?5 cm^?3, (8.5±3.3)×10^?6 cm^?3, and (1.08±0.49)×10^?7 cm^?3, respectively, assuming the He density is 0.0148±0.002 cm^?3.     

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

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

Isotopic Composition of H,HE and NE in the Protosolar Cloud

Observations and measurements in the solar wind, the Jovian atmosphere and the gases trapped in lunar surface material provide the main evidence from which the isotopic composition of H, He and Ne in the Protosolar Cloud (PSC) is derived. These measurements and observations are reviewed and the corrections are discussed that are needed for obtaining from them the PSC isotopic ratios. The D/H, ³He/⁴He (D+³He)/H, ²⁰Ne/²²Ne and ²¹Ne/²²Ne ratios adopted for the PSC are presented. Protosolar abundances provide the basis for the interpretation of isotopic ratios measured in the various solar system objects. In this article we discuss constraints derived from the PSC abundances on solar mixing, the origin of atmospheric neon, and the nature of the “SEP” component of neon trapped at the lunar surface. We also discuss constraints on the galactic evolution provided by the isotopic abundances of H and He in the PSC. This revised version was published online in August 2006 with corrections to the Cover Date.     

ROMAP: Rosetta Magnetometer and Plasma Monitor

The scientific objectives, design and capabilities of the Rosetta Lander’s ROMAP instrument are presented. ROMAP’s main scientific goals are longterm magnetic field and plasma measurements of the surface of Comet 67P/Churyumov-Gerasimenko in order to study cometary activity as a function of heliocentric distance, and measurements during the Lander’s descent to investigate the structure of the comet’s remanent magnetisation. The ROMAP fluxgate magnetometer, electrostatic analyser and Faraday cup measure the magnetic field from 0 to 32 Hz, ions of up to 8000 keV and electrons of up to 4200 keV. Additional two types of pressure sensors – Penning and Minipirani – cover a pressure range from 10⁻⁸ to 10¹ mbar. ROMAP’s sensors and electronics are highly integrated, as required by a combined field/plasma instrument with less than 1 W power consumption and 1 kg mass.     

Formation and Composition of Planetesimals

The composition of planetesimals depends upon the epoch and the location of their formation in the solar nebula. Meteorites produced in the hot inner nebula contain refractory compounds. Volatiles were present in icy planetesimals and cometesimals produced in the cold outer nebula. However, the mechanism responsible for their trapping is still controversial. We argue for a general scenario valid in all regions of the turbulent nebula where water condensed as a crystalline ice (Hersant et al., 2004). Volatiles were trapped in the form of clathrate hydrates in the continuously cooling nebula. The epoch of clathration of a given species depends upon the temperature and the pressure required for the stability of the clathrate hydrate. The efficiency of the mechanism depends upon the local amount of ice available. This scenario is the only one so far which proposes a quantitative interpretation of the non detection of N₂ in several comets of the Oort cloud (Iro et al., 2003). It may explain the large variation of the CO abundance observed in comets and predicts an Ar/O ratio much less than the upper limit of 0.1 times the solar ratio estimated on C/2001 A2 (Weaver et al., 2002). Under the assumption that the amount of water ice present at 5 AU was higher than the value corresponding to the solar O/H ratio by a factor 2.2 at least, the clathration scenario reproduces the quasi uniform enrichment with respect to solar of the Ar, Kr, Xe, C, N and S elements measured in Jupiter by the Galileo probe. The interpretation of the non-uniform enrichment in C, N and S in Saturn requires that ice was less abundant at 10 AU than at 5 AU so that CO and N₂ were not clathrated in the feeding zone of the planet while CH₄, NH₃ and H₂S were. As a result, the 14N/15N ratio in Saturn should be intermediate between that in Jupiter and the terrestrial ratio. Ar and Kr should be solar while Xe should be enriched by a factor 17. The enrichments in C, N and S in Uranus and Neptune suggest that available ice was able to form clathrates of CH₄, CO and the NH₃ hydrate, but not the clathrate of N₂. The enrichment of oxygen by a factor 440 in Neptune inferred by Lodders and Fegley (1994) from the detection of CO in the troposphere of the planet is higher by at least a factor 2.5 than the lower limit of O/H required for the clathration of CO and CH4 and for the hydration of NH₃. If CO detected by Encrenaz et al. (2004) in Uranus originates from the interior of the planet, the O/H ratio in the envelope must be around of order of 260 times the solar ratio, then also consistent with the trapping of detected volatiles by clathration. It is predicted that Ar and Kr are solar in the two planets while Xe would be enriched by a factor 30 to 70. Observational tests of the validity of the clathration scenario are proposed.