Isotopic Signatures of Volatiles in Terrestrial Planets - Working Group Report

Variations in the isotopic ratios of volatile elements in different reservoirs on the terrestrial planets carry information about processes that operated on the planets since their formation. Comparisons between primordial planetary compositions, to the extent they can be determined, may help us understand the planetary formation process. This working group report summarizes our knowledge of terrestrial planet volatile inventories. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Delivery of Water During Terrestrial Planet Formation

The planetary building blocks that formed in the terrestrial planet region were likely very dry, yet water is comparatively abundant on Earth. Here we review the various mechanisms proposed for the origin of water on the terrestrial planets. Various in-situ mechanisms have been suggested, which allow for the incorporation of water into the local planetesimals in the terrestrial planet region or into the planets themselves from local sources, although all of those mechanisms have difficulties. Comets have also been proposed as a source, although there may be problems fitting isotopic constraints, and the delivery efficiency is very low, such that it may be difficult to deliver even a single Earth ocean of water this way. The most promising route for water delivery is the accretion of material from beyond the snow line, similar to carbonaceous chondrites, that is scattered into the terrestrial planet region as the planets are growing. Two main scenarios are discussed in detail. First is the classical scenario in which the giant planets begin roughly in their final locations and the disk of planetesimals and embryos in the terrestrial planet region extends all the way into the outer asteroid belt region. Second is the Grand Tack scenario, where early inward and outward migration of the giant planets implants material from beyond the snow line into the asteroid belt and terrestrial planet region, where it can be accreted by the growing planets. Sufficient water is delivered to the terrestrial planets in both scenarios. While the Grand Tack scenario provides a better fit to most constraints, namely the small mass of Mars, planets may form too fast in the nominal case discussed here. This discrepancy may be reduced as a wider range of initial conditions is explored. Finally, we discuss several more recent models that may have important implications for water delivery to the terrestrial planets.     

Feedstocks of the Terrestrial Planets

The processes of planet formation in our Solar System resulted in a final product of a small number of discreet planets and planetesimals characterized by clear compositional distinctions. A key advance on this subject was provided when nucleosynthetic isotopic variability was discovered between different meteorite groups and the terrestrial planets. This information has now been coupled with theoretical models of planetesimal growth and giant planet migration to better understand the nature of the materials accumulated into the terrestrial planets. First order conclusions include that carbonaceous chondrites appear to contribute a much smaller mass fraction to the terrestrial planets than previously suspected, that gas-driven giant planet migration could have pushed volatile-rich material into the inner Solar System, and that planetesimal formation was occurring on a sufficiently rapid time scale that global melting of asteroid-sized objects was instigated by radioactive decay of ²⁶Al. The isotopic evidence highlights the important role of enstatite chondrites, or something with their mix of nucleosynthetic components, as feedstock for the terrestrial planets. A common degree of depletion of moderately volatile elements in the terrestrial planets points to a mechanism that can effectively separate volatile and refractory elements over a spatial scale the size of the whole inner Solar System. The large variability in iron to silicon ratios between both different meteorite groups and between the terrestrial planets suggests that mechanisms that can segregate iron metal from silicate should be given greater importance in future investigations. Such processes likely include both density separation of small grains in the nebula, but also preferential impact erosion of either the mantle or core from differentiated planets/planetesimals. The latter highlights the important role for giant impacts and collisional erosion during the late stages of planet formation.     

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 Formation of Mars: Building Blocks and Accretion Time Scale

In this review paper I address the current knowledge of the formation of Mars, focusing on its primary constituents, its formation time scale and its small mass compared to Earth and Venus. I argue that the small mass of Mars requires the terrestrial planets to have formed from a narrow annulus of material, rather than a disc extending to Jupiter. The truncation of the outer edge of the disc was most likely the result of giant planet migration, which kept Mars’ mass small. From cosmochemical constraints it is argued that Mars formed in a couple of million years and is essentially a planetary embryo that never grew to a full-fledged planet. This is in agreement with the latest dynamical models. Most of Mars’ building blocks consists of material that formed in the 2 AU to 3 AU region, and is thus more water-rich than that accreted by Earth and Venus. The putative Mars could have consisted of 0.1 % to 0.2 % by mass of water.     

Atmosphere Impact Losses

Determining the origin of volatiles on terrestrial planets and quantifying atmospheric loss during planet formation is crucial for understanding the history and evolution of planetary atmospheres. Using geochemical observations of noble gases and major volatiles we determine what the present day inventory of volatiles tells us about the sources, the accretion process and the early differentiation of the Earth. We further quantify the key volatile loss mechanisms and the atmospheric loss history during Earth’s formation. Volatiles were accreted throughout the Earth’s formation, but Earth’s early accretion history was volatile poor. Although nebular Ne and possible H in the deep mantle might be a fingerprint of this early accretion, most of the mantle does not remember this signature implying that volatile loss occurred during accretion. Present day geochemistry of volatiles shows no evidence of hydrodynamic escape as the isotopic compositions of most volatiles are chondritic. This suggests that atmospheric loss generated by impacts played a major role during Earth’s formation. While many of the volatiles have chondritic isotopic ratios, their relative abundances are certainly not chondritic again suggesting volatile loss tied to impacts. Geochemical evidence of atmospheric loss comes from the \({}^{3}\mathrm{He}/{}^{22}\mathrm{Ne}\), halogen ratios (e.g., F/Cl) and low H/N ratios. In addition, the geochemical ratios indicate that most of the water could have been delivered prior to the Moon forming impact and that the Moon forming impact did not drive off the ocean. Given the importance of impacts in determining the volatile budget of the Earth we examine the contributions to atmospheric loss from both small and large impacts. We find that atmospheric mass loss due to impacts can be characterized into three different regimes: 1) Giant Impacts, that create a strong shock transversing the whole planet and that can lead to atmospheric loss globally. 2) Large enough impactors (\(m_{\mathit{cap}} \gtrsim \sqrt{2} \rho_{0} (\pi h R)^{3/2}\), \(r_{\mathit{cap}}\sim25~\mbox{km}\) for the current Earth), that are able to eject all the atmosphere above the tangent plane of the impact site, where \(h\), \(R\) and \(\rho_{0}\) are the atmospheric scale height, radius of the target, and its atmospheric density at the ground. 3) Small impactors (\(m_{\mathit{min}}>4 \pi\rho_{0} h^{3}\), \(r_{\mathit {min}}\sim 1~\mbox{km}\) for the current Earth), that are only able to eject a fraction of the atmospheric mass above the tangent plane. We demonstrate that per unit impactor mass, small impactors with \(r_{\mathit{min}} < r < r_{\mathit{cap}}\) are the most efficient impactors in eroding the atmosphere. In fact for the current atmospheric mass of the Earth, they are more than five orders of magnitude more efficient (per unit impactor mass) than giant impacts, implying that atmospheric mass loss must have been common. The enormous atmospheric mass loss efficiency of small impactors is due to the fact that most of their impact energy and momentum is directly available for local mass loss, where as in the giant impact regime a lot of energy and momentum is ’wasted’ by having to create a strong shock that can transverse the entirety of the planet such that global atmospheric loss can be achieved. In the absence of any volatile delivery and outgassing, we show that the population of late impactors inferred from the lunar cratering record containing 0.1% \(M_{\oplus }\) is able to erode the entire current Earth’s atmosphere implying that an interplay of erosion, outgassing and volatile delivery is likely responsible for determining the atmospheric mass and composition of the early Earth. Combining geochemical observations with impact models suggest an interesting synergy between small and big impacts, where giant impacts create large magma oceans and small and larger impacts drive the atmospheric loss.     

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.     

Characteristic γ- and X-radiation in the planetary system

Conclusions Passive observation of the naturally occurring γ-ray and X-ray from the planets is potentially an important technique for determining their gross chemical composition and on the basis of natural γ-radiation determining if the planetary surface is composed of differential material. If the planet is not covered by a thick atmosphere then it is possible to map the distribution of the most abundant elements on a scale of spatial resolution that is of the order of the altitude at which the observations are made. Initial observations carried out from lunar orbit have shown that the flux levels are approximately as expected and that the lunar surface is not characterized by any widespread distribution of acidic rocks in the region observed by the Luna 10 spacecraft.     

Creating Habitable Zones, at all Scales, from Planets to Mud Micro-Habitats, on Earth and on Mars

The factors that create a habitable planet are considered at all scales, from planetary inventories to micro-habitats in soft sediments and intangibles such as habitat linkage. The possibility of habitability first comes about during accretion, as a product of the processes of impact and volatile inventory history. To create habitability water is essential, not only for life but to aid the continual tectonic reworking and erosion that supply key redox contrasts and biochemical substrates to sustain habitability. Mud or soft sediment may be a biochemical prerequisite, to provide accessible substrate and protection. Once life begins, the habitat is widened by the activity of life, both by its management of the greenhouse and by partitioning reductants (e.g. dead organic matter) and oxidants (including waste products). Potential Martian habitats are discussed: by comparison with Earth there are many potential environmental settings on Mars in which life may once have occurred, or may even continue to exist. The long-term evolution of habitability in the Solar System is considered.     

Astrobiology and habitability of Titan

Largest satellite of Saturn and the only in the solar system having a dense atmosphere, Titan is one of the key planetary bodies for astrobiological studies, due to several aspects. (i) Its analogies with planet Earth, in spite of much lower temperatures, with, in particular, a methane cycle on Titan analogous to the water cycle on Earth. (ii) The presence of an active organic chemistry, involving several of the key compounds of prebiotic chemistry. The recent data obtained from the Huygens instruments show that the complex organic matter in Titan’s low atmosphere is mainly concentrated in the aerosol particles. The formation of biologically interesting compounds may also occur in the deep water ocean, from the hydrolysis of complex organic material included in the chrondritic matter accreted during the formation of Titan. (iii) The possible emergence and persistence of Life on Titan. All ingredients which seem necessary for Life to appear and even develop – liquid water, organic matter and energy – are present on Titan. Consequently, it cannot be excluded that life may have emerged on or in Titan. In spite of the extreme conditions in this environment life may have been able to adapt and to persist. Many data are still expected from the Cassini-Huygens mission and future astrobiological exploration mission of Titan are now under consideration. Nevertheless, Titan already looks like another world, with an active organic chemistry, in the absence of permanent liquid water, on the surface: a natural laboratory for prebiotic-like chemistry.     

HED Meteorites and Their Relationship to the Geology of Vesta and the Dawn Mission

Howardite-eucrite-diogenite (HED) meteorites, thought to be derived from 4 Vesta, provide the best sampling available for any differentiated asteroid. However, deviations in oxygen isotopic composition from a common mass-fractionation line suggest that a few eucrite-like meteorites are from other bodies, or that Vesta was not completely homogenized during differentiation. The petrology and geochemistry of HEDs provide insights into igneous processes that produced a crust composed of basalts, gabbros, and ultramafic cumulate rocks. Although most HED magmas were fractionated, it is unresolved whether some eucrites may have been primary melts. The geochemistry of HEDs indicates that bulk Vesta is depleted in volatile elements and is relatively reduced, but has chondritic refractory element abundances. The compositions of HEDs may favor a magma ocean model, but inconsistencies remain. Geochronology indicates that Vesta accreted and differentiated within the first several million years of solar system history, that magmatism continued over a span of ??10 Myr, and that its thermal history extended for perhaps 100 Myr. The protracted cooling history is probably responsible for thermal metamorphism of most HEDs. Impact chronology indicates that Vesta experienced many significant collisions, including during the late heavy bombardment. The age of the huge south pole crater is controversial, but it probably ejected Vestoids and many HEDs. Continued impacts produced a regolith composed of eucrite and diogenite fragments containing only minor exotic materials. HED meteorites serve as ground truth for orbital spectroscopic and chemical analyses by the Dawn spacecraft, and their properties are critical for instrument calibration and interpretation of Vesta??s geologic history.     

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.     

Chemistry,accretion, and evolution of Mars

The high FeO concentrations measured by VIKING for the Martian soils correspond to all probability to a FeO-rich mantle. In general, the VIKING XRF-data indicate a mafic crust with a considerably smaller degree of fractionation compared to the terrestrial crust.In recent years evidence has been collected which points towards Mars being the parent body of SNC-meteorites and, hence, these meteorites have become a valuable source of information about the chemistry of Mars. Using element correlations observed in SNC-meteorites and general cosmochemical constraints, it is possible to estimated the bulk composition of Mars. Normalized to Si and Cl, the mean abundance value for the elements Ga, Fe, Na, P, K, F, and Rb in the Martian mantle is found to be 0.35 and thus exceeds the terrestrial value by about a factor of two. Aside pressure effects and the H₂O poverty, the high P and K content of the Martian mantle may lead to magmatic processes different from those on Earth.The composition of the Earth's mantle can successfully be described by a two component model. Component A: highly reduced and almost free of all elements more volatile than Na; component B: oxidized and containing all elements in Cl-abundances including volatile elements. The same two components can be used as building blocks for Mars, if one assumes that, contrary to the inhomogeneous accretion of the Earth, Mars accreted almost homogeneously. The striking depletion of all elements with chalcophile character indicates that chemical equilibrium between component A and B was achieved on Mars which lead to the formation of significant amounts of FeS which, on segregation, extracted the elements according to their sulphide-silicate partition coefficients. While for the Earth a mixing ratio AB = 8515 was derived, the Mars ratio of 6040 reflects the higher concentrations of moderately volatile elements like Na, K, and sulphur on Mars. A homogeneous accretion of Mars could also explain the obvious low abundances of water and primordial rare gases.     

Water Reservoirs in Small Planetary Bodies: Meteorites,Asteroids, and Comets

Asteroids and comets are the remnants of the swarm of planetesimals from which the planets ultimately formed, and they retain records of processes that operated prior to and during planet formation. They are also likely the sources of most of the water and other volatiles accreted by Earth. In this review, we discuss the nature and probable origins of asteroids and comets based on data from remote observations, in situ measurements by spacecraft, and laboratory analyses of meteorites derived from asteroids. The asteroidal parent bodies of meteorites formed \(\leq 4\) Ma after Solar System formation while there was still a gas disk present. It seems increasingly likely that the parent bodies of meteorites spectroscopically linked with the E-, S-, M- and V-type asteroids formed sunward of Jupiter’s orbit, while those associated with C- and, possibly, D-type asteroids formed further out, beyond Jupiter but probably not beyond Saturn’s orbit. Comets formed further from the Sun than any of the meteorite parent bodies, and retain much higher abundances of interstellar material. CI and CM group meteorites are probably related to the most common C-type asteroids, and based on isotopic evidence they, rather than comets, are the most likely sources of the H and N accreted by the terrestrial planets. However, comets may have been major sources of the noble gases accreted by Earth and Venus. Possible constraints that these observations can place on models of giant planet formation and migration are explored.     

Cosmic-ray Composition as Observed by Ulysses

The cosmic ray isotopic composition measurements from the High Energy Telescope (HET) on the Ulysses spacecraft are reviewed. The source isotopic composition of key elements is found to be surprisingly like the Solar system abundances with the notable exception of ²²Ne. The average density of interstellar material cosmic rays traverse is found to be 0.25 atom cm^–3, corresponding to a confinement time of 20 Myr. Vanadium isotopic abundances are shown to be consistent with weak cosmic-ray reacceleration. The implications of these measurements are discussed.     

HF-W Chronometry and Inner Solar System Accretion Rates

Models for the mechanisms of accretion of the terrestrial planets are re-examined using the experimental technique of high-precision isotope ratio mass spectrometry of tungsten (W). The decay of ¹⁸²Hf to ¹⁸²W (via ¹⁸²Ta) provides a new kind of radiometric chronometer of planet formation processes. Hafnium and W, the parent and daughter trace elements, are highly refractory; however, Hf is lithophile and strongly partitioned into the silicate portion of a planet, whereas W is moderately siderophile and preferentially partitioned into a coexisting metallic phase. More than 90% of terrestrial W has gone into the Earth's core during its formation. The residual silicate portion, the Earth's primitive mantle, has a Hf/W ratio in the range 10−40, an order of magnitude higher than chondritic (∼1.3). Tungsten isotopic data for the Earth and the Moon suggest that we can date a major event of planet formation: The Moon formed about 50 Myrs after the start of the solar system, providing strong support for the Giant Impact Theory of lunar origin. Recent simulations of this event imply that the Earth was probably only half formed at the time. From this we can deduce the planetary accretion rate. Tungsten isotope data for Mars provide evidence of a much shorter accretion interval, perhaps as little as 10 Myrs, but the rates for the Earth over the same time interval could have been comparable. The large W isotopic heterogeneities on Mars could only have been produced within the first 30 Myrs of the solar system. Large-scale mixing, e.g. from convective overturn, as is thought to drive the Earth's plates, must be absent from Mars. Limitations of the method such as 1) cosmogenic ¹⁸²Ta effects on lunar samples, 2) incomplete mixing of debris to cause W isotope heterogeneity on the Moon, and 3) initial ¹⁸²Hf/¹⁸⁰Hf heterogeneities of the early solar system are critically discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Evolution of the Protosolar Nebula and Formation of the Giant Planets

The formation of planetary systems is intimately tied to the question of the evolution of the gas and solid material in the early nebula. Current models of evolution of circumstellar disks are reviewed here with emphasis on the so-called “alpha models” in which angular momentum is transported outward by turbulent viscosity, parameterized by an dimensionless parameter α. A simple 1D model of protoplanetary disks that includes gas and embedded particles is used to introduce key questions on planetesimal formation. This model includes the aerodynamic properties of solid ice and rock grains to calculate their migration and growth. We show that the evolution of the nebula and migration and growth of its solids proceed on timescales that are generally not much longer than the timescale necessary to fully form the star-disk system from the molecular cloud. Contrary to a widely used approach, planet formation therefore can neither be studied in a static nebula nor in a nebula evolving from an arbitrary initial condition. We propose a simple approach to both account for sedimentation from the molecular cloud onto the disk, disk evolution and migration of solids. Giant planets have key roles in the history of the forming Solar System: they formed relatively early, when a significant amount of hydrogen and helium were still present in the nebula, and have a mass that is a sizable fraction of the disk mass at any given time. Their composition is also of interest because when compared to the solar composition, their enrichment in elements other than hydrogen and helium is a witness of sorting processes that occured in the protosolar nebula. We review likely scenarios capable of explaining both the presence of central dense cores in Jupiter, Saturn, Uranus and Neptune and their global composition. This revised version was published online in August 2006 with corrections to the Cover Date.     

Isotopic Fractionation by Gravitational Escape

Present natural data bases for abundances of the isotopic compositions of noble gases, carbon and nitrogen inventories can be found in the Sun, the solar wind, meteorites and the planetary atmospheres and crustal reservoirs. Mass distributions in the various volatile reservoirs provide boundary conditions which must be satisfied in modelling the history of the present atmospheres. Such boundary conditions are constraints posed by comparison of isotopic ratios in primordial volatile sources with the isotopic pattern which was found on the planets and their satellites. Observations from space missions and Earth-based spectroscopic telescope observations of Venus, Mars and Saturn's major satellite Titan show that the atmospheric evolution of these planetary bodies to their present states was affected by processes capable of fractionating their elements and isotopes. The isotope ratios of D/H in the atmospheres of Venus and Mars indicate evidence for their planetary water inventories. Venus' H₂O content may have been at least 0.3% of a terrestrial ocean. Analysis of the D/H ratio on Mars imply that a global H₂O ocean with a depth of ≤ 30 m was lost since the end of hydrodynamic escape. Calculations of the time evolution of the ¹⁵N/¹⁴N isotope anomalies in the atmospheres of Mars and Titan show that the Martian atmosphere was at least ≥ 20 times denser than at present and that the mass of Titan's early atmosphere was about 30 times greater than its present value. A detailed study of gravitational fractionation of isotopes in planetary atmospheres furthermore indicates a much higher solar wind mass flux of the early Sun during the first half billion years. This revised version was published online in August 2006 with corrections to the Cover Date.     

Neutral Atmospheres of the Giant Planets: An Overview of Composition Measurements

Measurements of the chemical composition of the giant planets provide clues of their formation and evolution processes. According to the currently accepted nucleation model, giant planets formed from the initial accretion of an icy core and the capture of the protosolar gas, mosly composed of hydrogen and helium. In the case of Jupiter and Saturn (the gaseous giants), this gaseous component dominates the composition of the planet, while for Uranus and Neptune (the icy giants) it is only a small fraction of the total mass. The measurement of elemental and isotopic ratios in the giant planets provides key diagnostics of this model, as it implies an enrichment in heavy elements (as well as deuterium) with respect to the cosmic composition. Neutral atmospheric constituents in the giant planets have three possible sources: (1) internal (fromthe bulk composition of the planet), (2) photochemical (fromthe photolysis ofmethane) and(3) external (from meteoritic impacts, of local or interplanetary origin). This paper reviews our present knowledge about the atmospheric composition in the giant planets, and their elemental and istopic composition. Measurements concerning key parameters, like C/H, D/H or rare gases in Jupiter, are analysed in detail. The conclusion addresses open questions and observations to be performed in the future.     

Isotopes of Volatiles in Pre-Solar Grains

Elements usually considered volatile are key constituents (C, N, O) of the pre-solar grains identified in primitive meteorites and/or key diagnostic elements (noble gases). Their isotopic compositions generally are unlike anything seen in matter of solar-system origin. The large variations are indicative of the various stellar sources and various processes of nucleosynthesis by which they were created. This revised version was published online in August 2006 with corrections to the Cover Date.