Light elements and their isotopes in SNC meteorites and the Martian atmosphere

Nitrogen isotopes have played an important part in the acceptance of the hypothesis that SNC meteorites derive from Mars. As a result, these meteorites can be investigated for their carbon, sulphur, and hydrogen systematics with a view to learning something about the environmental conditions on the planet. Important aspects of the role of carbon, present in the form of carbon dioxide as an atmospheric gas and leading to the formation of carbonates by weathering or hydrothermal activity, can be established. The presence of indigenous organics is an intriguing possibility. A variety of new or emerging techniques which could improve our understanding of SNC meteorites and might be applied to a returned Martian sample are discussed.     

Core Formation and Mantle Differentiation on Mars

Geochemical investigation of Martian meteorites (SNC meteorites) yields important constraints on the chemical and geodynamical evolution of Mars. These samples may not be representative of the whole of Mars; however, they provide constraints on the early differentiation processes on Mars. The bulk composition of Martian samples implies the presence of a metallic core that formed concurrently as the planet accreted. The strong depletion of highly siderophile elements in the Martian mantle is only possible if Mars had a large scale magma ocean early in its history allowing efficient separation of a metallic melt from molten silicate. The solidification of the magma ocean created chemical heterogeneities whose ancient origin is manifested in the heterogeneous ¹⁴²Nd and ¹⁸²W abundances observed in different meteorite groups derived from Mars. The isotope anomalies measured in SNC meteorites imply major chemical fractionation within the Martian mantle during the life time of the short-lived isotopes ¹⁴⁶Sm and ¹⁸²Hf. The Hf-W data are consistent with very rapid accretion of Mars within a few million years or, alternatively, a more protracted accretion history involving several large impacts and incomplete metal-silicate equilibration during core formation. In contrast to Earth early-formed chemical heterogeneities are still preserved on Mars, albeit slightly modified by mixing processes. The preservation of such ancient chemical differences is only possible if Mars did not undergo efficient whole mantle convection or vigorous plate tectonic style processes after the first few tens of millions of years of its history.     

The Accretion, Composition and Early Differentiation of Mars

The early development of Mars is of enormous interest, not just in its own right, but also because it provides unique insights into the earliest history of the Earth, a planet whose origins have been all but obliterated. Mars is not as depleted in moderately volatile elements as are other terrestrial planets. Judging by the data for Martian meteorites it has Rb/Sr 0.07 and K/U 19,000, both of which are roughly twice as high as the values for the Earth. The mantle of Mars is also twice as rich in Fe as the mantle of the Earth, the Martian core being small (20% by mass). This is thought to be because conditions were more oxidizing during core formation. For the same reason a number of elements that are moderately siderophile on Earth such as P, Mn, Cr and W, are more lithophile on Mars. The very different apparent behavior of high field strength (HFS) elements in Martian magmas compared to terrestrial basalts and eucrites may be related to this higher phosphorus content. The highly siderophile element abundance patterns have been interpreted as reflecting strong partitioning during core formation in a magma ocean environment with little if any late veneer. Oxygen isotope data provide evidence for the relative proportions of chondritic components that were accreted to form Mars. However, the amount of volatile element depletion predicted from these models does not match that observed — Mars would be expected to be more depleted in volatiles than the Earth. The easiest way to reconcile these data is for the Earth to have lost a fraction of its moderately volatile elements during late accretionary events, such as giant impacts. This might also explain the non-chondritic Si/Mg ratio of the silicate portion of the Earth. The lower density of Mars is consistent with this interpretation, as are isotopic data. ⁸⁷Rb-⁸⁷Sr, ¹²⁹I-¹²⁹Xe, ¹⁴⁶Sm-¹⁴²Nd, ¹⁸²Hf-¹⁸²W, ¹⁸⁷Re-¹⁸⁷Os, ²³⁵U-²⁰⁷Pb and ²³⁸U-²⁰⁶Pb isotopic data for Martian meteorites all provide evidence that Mars accreted rapidly and at an early stage differentiated into atmosphere, mantle and core. Variations in heavy xenon isotopes have proved complicated to interpret in terms of ²⁴⁴Pu decay and timing because of fractionation thought to be caused by hydrodynamic escape. There are, as yet, no resolvable isotopic heterogeneities identified in Martian meteorites resulting from ⁹²Nb decay to ⁹²Zr, consistent with the paucity of perovskite in the martian interior and its probable absence from any Martian magma ocean. Similarly the longer-lived ¹⁷⁶Lu-¹⁷⁶Hf system also preserves little record of early differentiation. In contrast W isotope data, Ba/W and time-integrated Re/Os ratios of Martian meteorites provide powerful evidence that the mantle retains remarkably early heterogeneities that are vestiges of core metal segregation processes that occurred within the first 20 Myr of the Solar System. Despite this evidence for rapid accretion and differentiation, there is no evidence that Mars grew more quickly than the Earth at an equivalent size. Mars appears to have just stopped growing earlier because it did not undergo late stage (>20 Myr), impacts on the scale of the Moon-forming Giant Impact that affected the Earth.     

Cratering Chronology and the Evolution of Mars

Results by Neukum et al. (2001) and Ivanov (2001) are combined with crater counts to estimate ages of Martian surfaces. These results are combined with studies of Martian meteorites (Nyquist et al., 2001) to establish a rough chronology of Martian history. High crater densities in some areas, together with the existence of a 4.5 Gyr rock from Mars (ALH84001), which was weathered at about 4.0 Gyr, affirm that some of the oldest surfaces involve primordial crustal materials, degraded by various processes including megaregolith formation and cementing of debris. Small craters have been lost by these processes, as shown by comparison with Phobos and with the production function, and by crater morphology distributions. Crater loss rates and survival lifetimes are estimated as a measure of average depositional/erosional rate of activity.We use our results to date the Martian epochs defined by Tanaka (1986). The high crater densities of the Noachian confine the entire Noachian Period to before about 3.5 Gyr. The Hesperian/Amazonian boundary is estimated to be about 2.9 to 3.3 Gyr ago, but with less probability could range from 2.0 to 3.4 Gyr. Mid-age dates are less well constrained due to uncertainties in the Martian cratering rate. Comparison of our ages with resurfacing data of Tanaka et al. (1987) gives a strong indication that volcanic, fluvial, and periglacial resurfacing rates were all much higher in approximately the first third of Martian history. We estimate that the Late Amazonian Epoch began a few hundred Myr ago (formal solutions 300 to 600 Myr ago). Our work supports Mariner 9 era suggestions of very young lavas on Mars, and is consistent with meteorite evidence for Martian igneous rocks 1.3 and 0.2 – 0.3 Gyr old. The youngest detected Martian lava flows give formal crater retention ages of the order 10 Myr or less. We note also that certain Martian meteorites indicate fluvial activity younger than the rock themselves, 700 Myr in one case, and this is supported by evidence of youthful water seeps. The evidence of youthful volcanic and aqueous activity, from both crater-count and meteorite evidence, places important constraints on Martian geological evolution and suggests a more active, complex Mars than has been visualized by some researchers.     

Origin,age, and composition of meteorites

This paper attempts to bring together and evaluate all significant evidence on the origin of meteorites.The iron meteorites seem to have formed at low pressures. Laboratory evidence shows that the absence of a Widmanstätten pattern in meteorites with > 16% Ni cannot be attributed to high pressures, but to supercooling or an unusually fast cooling rate for these meteorites, which prevented the development of a pattern. The presence of tridymite in the Steinbach siderophyre provides further, direct proof that the Widmanstätten pattern can form at pressures less than 3 kb. Neither diamond, nor cliftonite, nor cohenite are reliable pressure indicators in meteorites. Diamonds were formed by shock while cliftonite may have been derived from a cubic carbide such as Fe₄C. Cohenite is apparently stabilized by kinetic rather than thermodynamic factors. Several lines of evidence suggest that the irons come from more than one parent body, perhaps as many as four.The frequency of pallasites is perfectly consistent with an origin in the transition zone between core and mantle of the parent body. Hybrid meteorites such as Brenham are not necessarily derived from the metal-silicate interface, but probably resulted from dendrite growth in the solidifying melt.Ordinary chondrites definitely are equilibrium assemblages rather than chance conglomerates. According to the best available evidence, Prior's rules seem to be valid. The metal particles in chondrites differentiated into kamacite and taenite in their present location, rather than in a remote earlier environment. Trace element abundances in ordinary and carbonaceous chondrites suggest that these meteorites accreted from two types of matter: an undepleted fraction that separated from its complement of gases at low temperatures, and a depleted fraction that lost its gases at high temperatures. These two fractions of primitive meteoritic matter are tentatively identified with the matrix and chondrules-plus-metal, respectively. New restrictive limits are placed on the iron-silicate fractionation in chondrites. No direct evolutionary path exists that connects the currently accepted solar abundances of Fe and Ni and the observed Fe/Si and Ni/Si ratios in chondrites. Apparently the solar abundance of iron is in error. The iron-silicate fractionation seems to have occurred while chondritic matter was in a more strongly reduced state than its present one.The U-He and K-Ar ages of hypersthene chondrites are systematically shorter than those of bronzite chondrites. Short ages are correlated with shock effects, and it seems that the hypersthene chondrites suffered reheating and partial-to-complete outgassing 0.4 AE ago. The cosmic-ray exposure ages of all classes of meteorites cluster distinctly, indicating that the meteorites were produced in a few discrete major collisions rather than by a quasi-continuum of smaller ones. The dates of the principal breakups are: irons, 0.6 and 0.9 AE; aubrites, 45 m.y.; bronzite chondrites, 4 m.y.; hypersthene chondrites, 0.025, 3, 7–13, and 16–31 m.y. All four clusters of hypersthene chondrites show evidence of severe outgassing 0.4 AE ago, which implies that most or all hypersthene chondrites come from the same parent body.As already noted by Signer and Suess, two distinct types of primordial gas occur in meteorites. Differentiated meteorites always contain unfractionated gas, while relatively undifferentiated meteorites contain fractionated gas. The former component is invariably associated with shock effects, and seems to have been derived from the solar wind. The latter component is correlated with other volatiles and seems to be a truly primitive constituent of meteoritic matter. Isotopic anomalies in the fractionated gas suggest that meteoritic matter was irradiated with 10¹⁷ protons/cm² at a very early stage of its history.There is very little doubt that most, if not all, meteorites come from the asteroid belt rather than from the moon. The orbits and geocentric velocities of stony meteorites resemble those of the Apollo asteroids (most of which are former members of the asteroid belt that have strayed into terrestrial space), but disagree strongly with the calculated orbits and velocities for lunar ejecta. Öpik's conclusions about the difficulty of accelerating lunar debris to escape velocity represent a further argument against a lunar origin of stony meteorites.The most likely parent bodies of the meteorites are the 34 asteroids which cross the orbit of Mars. Collisional debris from these objects will remain in Mars-crossing orbits, and perturbations by Mars will inject some fraction of this material into terrestrial space. Most of the Mars asteroids, comprising 98% of the mass and 92% of the cross-section, belong to three Hirayama families (Phocaea, Desiderata, and Aethra), and an additional, previously unrecognized family. These families were apparently produced by disruption of parent asteroids ca. 104, 105, and 46 km in diameter. The size distribution and light curves of asteroids indicate that the larger asteroids are original accretions, rather than collision fragments. There is no reason to believe that the meteorites ever resided in bodies larger than Ceres (d = 770 km).Various theories on the origin of the meteorites are critically reviewed in the light of the preceding evidence. Wood's theory, which postulates a high-temperature and a low-temperature variety of primordial matter, is in best accord with the evidence. Apparently the asteroids accreted from varying proportions of these two types of material, and were then heated by extinct radioactivity produced in the early irradiation.     

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.     

Calibration of the Mars Science Laboratory Alpha Particle X-ray Spectrometer

The alpha-particle X-ray spectrometer (APXS) for the Mars Science Laboratory (MSL) mission was calibrated for routine analysis of: Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Zn, Br, Rb, Sr, and Y. The following elements were also calibrated, but may be too low to be measured (10s–100s ppm) for their usual abundance on Mars: V, Cu, Ga, As, Se and W. An extensive suite of geological reference materials, supplemented by pure chemical elements and compounds was used. Special attention was paid to include phyllosilicates, sulfates and a broad selection of basalts as these are predicted minerals and rocks at the Gale Crater landing site. The calibration approach is from first principles, using fundamental physics parameters and an assumed homogeneous sample matrix to calculate expected elemental signals for a given instrument setup and sample composition. Resulting concentrations for most elements accord with expected values. Deviations in elements of lower atomic number (Na, Mg, Al) indicate significant influences of mineral phases, especially in basalts, ultramafic rocks and trachytes. The systematics of these deviations help us to derive empirical, iterative corrections for different rock groups, based on a preliminary APXS analysis which assumes a homogeneous sample. These corrections have the potential to significantly improve the accuracy of APXS analyses, especially when other MSL instrument results, such as the X-ray diffraction data from CheMin, are included in the overall analysis process.     

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.     

Ages and Geologic Histories of Martian Meteorites

We review the radiometric ages of the 16 currently known Martian meteorites, classified as 11 shergottites (8 basaltic and 3 lherzolitic), 3 nakhlites (clinopyroxenites), Chassigny (a dunite), and the orthopyroxenite ALH84001. The basaltic shergottites represent surface lava flows, the others magmas that solidified at depth. Shock effects correlate with these compositional types, and, in each case, they can be attributed to a single shock event, most likely the meteorite's ejection from Mars. Peak pressures in the range 15 – 45 GPa appear to be a "launch window": shergottites experienced ～30 – 45 GPa, nakhlites ～20 ± 5 GPa, Chassigny ～35 GPa, and ALH84001 ～35 – 40 GPa. Two meteorites, lherzolitic shergottite Y-793605 and orthopyroxenite ALH84001, are monomict breccias, indicating a two-phase shock history in toto: monomict brecciation at depth in a first impact and later shock metamorphism in a second impact, probably the ejection event. Crystallization ages of shergottites show only two pronounced groups designated S₁ (～175 Myr), including 4 of 6 dated basalts and all 3 lherzolites, and S₂ (330 – 475 Myr), including two basaltic shergottites and probably a third according to preliminary data. Ejection ages of shergottites, defined as the sum of their cosmic ray exposure ages and their terrestrial residence ages, range from the oldest (～20 Myr) to the youngest (～0.7 Myr) values for Martian meteorites. Five groups are distinguished and designated S_Dho (one basalt, ～20 Myr), S_L (two lherzolites of overlapping ejection ages, 3.94 ± 0.40 Myr and 4.70 ± 0.50 Myr), S (four basalts and one lherzolite, ～2.7 – 3.1 Myr), S_DaG (two basalts, ～1.25 Myr), and S_E (the youngest basalt, 0.73 ± 0.15 Myr). Consequently, crystallization age group S₁ includes ejection age groups S_L, S_E and 4 of the 5 members of S, whereas S₂ includes the remaining member of S and one of the two members of S_DaG. Shock effects are different for basalts and lherzolites in group S/S₁. Similarities to the dated meteorite DaG476 suggest that the two shergottites that are not dated yet belong to group S₂. Whether or not S₂ is a single group is unclear at present. If crystallization age group S₁ represents a single ejection event, pre-exposure on the Martian surface is required to account for ejection ages of S_L that are greater than ejection ages of S, whereas secondary breakup in space is required to account for ejection ages of S_E less than those of S. Because one member of crystallization age group S₂ belongs to ejection group S, the maximum number of shergottite ejection events is 6, whereas the minimum number is 2. Crystallization ages of nakhlites and Chassigny are concordant at ～1.3 Gyr. These meteorites also have concordant ejection ages, i.e., they were ejected together in a single event (NC). Shock effects vary within group NC between the nakhlites and Chassigny. The orthopyroxenite ALH84001 is characterized by the oldest crystallization age of ～4.5 Gyr. Its secondary carbonates are ～3.9 Gyr old, an age corresponding to the time of Ar-outgassing from silicates. Carbonate formation appears to have coincided with impact metamorphism, either directly, or indirectly, perhaps via precipitation from a transient impact crater lake. The crystallization age and the ejection age of ALH84001, the second oldest ejection age at 15.0 ± 0.8 Myr, give evidence for another ejection event (O). Consequently, the total number of ejection events for the 16 Martian meteorites lies in the range 4 – 8. The Martian meteorites indicate that Martian magmatism has been active over most of Martian geologic history, in agreement with the inferred very young ages of flood basalt flows observed in Elysium and Amazonis Planitia with the Mars Orbital Camera (MOC) on the Mars Global Surveyor (MGS). The provenance of the youngest meteorites must be found among the youngest volcanic surfaces on Mars, i.e., in the Tharsis, Amazonis, and Elysium regions.     

Long-Term Evolution of the Martian Crust-Mantle System

Lacking plate tectonics and crustal recycling, the long-term evolution of the crust-mantle system of Mars is driven by mantle convection, partial melting, and silicate differentiation. Volcanic landforms such as lava flows, shield volcanoes, volcanic cones, pyroclastic deposits, and dikes are observed on the martian surface, and while activity was widespread during the late Noachian and Hesperian, volcanism became more and more restricted to the Tharsis and Elysium provinces in the Amazonian period. Martian igneous rocks are predominantly basaltic in composition, and remote sensing data, in-situ data, and analysis of the SNC meteorites indicate that magma source regions were located at depths between 80 and 150 km, with degrees of partial melting ranging from 5 to 15 %. Furthermore, magma storage at depth appears to be of limited importance, and secular cooling rates of 30 to 40 K?Gyr^?1 were derived from surface chemistry for the Hesperian and Amazonian periods. These estimates are in general agreement with numerical models of the thermo-chemical evolution of Mars, which predict source region depths of 100 to 200 km, degrees of partial melting between 5 and 20 %, and secular cooling rates of 40 to 50 K?Gyr^?1. In addition, these model predictions largely agree with elastic lithosphere thickness estimates derived from gravity and topography data. Major unknowns related to the evolution of the crust-mantle system are the age of the shergottites, the planet’s initial bulk mantle water content, and its average crustal thickness. Analysis of the SNC meteorites, estimates of the elastic lithosphere thickness, as well as the fact that tidal dissipation takes place in the martian mantle indicate that rheologically significant amounts of water of a few tens of ppm are still present in the interior. However, the exact amount is controversial and estimates range from only a few to more than 200 ppm. Owing to the uncertain formation age of the shergottites it is unclear whether these water contents correspond to the ancient or present mantle. It therefore remains to be investigated whether petrologically significant amounts of water of more than 100 ppm are or have been present in the deep interior. Although models suggest that about 50 % of the incompatible species (H₂O, K, Th, U) have been removed from the mantle, the amount of mantle differentiation remains uncertain because the average crustal thickness is merely constrained to within a factor of two.     

Alteration Assemblages in Martian Meteorites: Implications for Near-Surface Processes

The SNC (Shergotty-Nakhla-Chassigny) meteorites have recorded interactions between martian crustal fluids and the parent igneous rocks. The resultant secondary minerals — which comprise up to 1 vol.% of the meteorites — provide information about the timing and nature of hydrous activity and atmospheric processes on Mars. We suggest that the most plausible models for secondary mineral formation involve the evaporation of low temperature (25 – 150 °C) brines. This is consistent with the simple mineralogy of these assemblages — Fe-Mg-Ca carbonates, anhydrite, gypsum, halite, clays — and the chemical fractionation of Ca-to Mg-rich carbonate in ALH84001 "rosettes". Longer-lived, and higher temperature, hydrothermal systems would have caused more silicate alteration than is seen and probably more complex mineral assemblages. Experimental and phase equilibria data on carbonate compositions similar to those present in the SNCs imply low temperatures of formation with cooling taking place over a short period of time (e.g. days). The ALH84001 carbonate also probably shows the effects of partial vapourisation and dehydration related to an impact event post-dating the initial precipitation. This shock event may have led to the formation of sulphide and some magnetite in the Fe-rich outer parts of the rosettes.Radiometric dating (K-Ar, Rb-Sr) of the secondary mineral assemblages in one of the nakhlites (Lafayette) suggests that they formed between 0 and 670 Myr, and certainly long after the crystallisation of the host igneous rocks. Crystallisation of ALH84001 carbonate took place 0.5 Gyr after the parent rock. These age ranges and the other research on these assemblages suggest that environmental conditions conducive to near-surface liquid water have been present on Mars periodically over the last 1 Gyr. This fluid activity cannot have been continuous over geological time because in that case much more silicate alteration would have taken place in the meteorite parent rocks and the soluble salts would probably not have been preserved.The secondary minerals could have been precipitated from brines with seawater-like composition, high bicarbonate contents and a weakly acidic nature. The co-existence of siderite (Fe-carbonate) and clays in the nakhlites suggests that the pCO₂ level in equilibrium with the parent brine may have been 50 mbar or more. The brines could have originated as flood waters which percolated through the top few hundred meters of the crust, releasing cations from the surrounding parent rocks. The high sulphur and chlorine concentrations of the martian soil have most likely resulted from aeolian redistribution of such aqueously-deposited salts and from reaction of the martian surface with volcanic acid volatiles.The volume of carbonates in meteorites provides a minimum crustal abundance and is equivalent to 50–250 mbar of CO₂ being trapped in the uppermost 200–1000 m of the martian crust. Large fractionations in ¹⁸O between igneous silicate in the meteorites and the secondary minerals (30) require formation of the latter below temperatures at which silicate-carbonate equilibration could have taken place (400°C) and have been taken to suggest low temperatures (e.g. 150°C) of precipitation from a hydrous fluid.     

The Martian stratigraphy — Short review and perspectives

The main aspects of the Martian stratigraphy have been determined from the detailed study of Mariner 9 and Viking Orbiter images. Three major stratigraphic systems, the Noachian System, the Hesperian System, and the Amazonian System, are inferred from these studies. The global geological evolution of Mars is essentially derived from its stratigraphy. It reveals that tectonism and volcanism were widespread during two major periods (Noachian and Lower Hesperian) and became more localized during the Upper Hesperian and Amazonian periods. The transition between these two major periods occurred about 2 Ga ago, and significant geologic activity could still be present. However, a number of geologic features and processes remain little understood. Future investigations, including complete high resolution imaging and detailed mapping, geochemical mapping, in situ chemical analyses, etc., will be necessary in order to improve our knowledge of the Martian stratigraphy and geologic evolution and are essential to prepare any future Mars Sample Return mission and the Human Exploration of this planet.     

Geochemical Consequences of Widespread Clay Mineral Formation in Mars’ Ancient Crust

Clays form on Earth by near-surface weathering, precipitation in water bodies within basins, hydrothermal alteration (volcanic- or impact-induced), diagenesis, metamorphism, and magmatic precipitation. Diverse clay minerals have been detected from orbital investigation of terrains on Mars and are globally distributed, indicating geographically widespread aqueous alteration. Clay assemblages within deep stratigraphic units in the Martian crust include Fe/Mg smectites, chlorites and higher temperature hydrated silicates. Sedimentary clay mineral assemblages include Fe/Mg smectites, kaolinite, and sulfate, carbonate, and chloride salts. Stratigraphic sequences with multiple clay-bearing units have an upper unit with Al-clays and a lower unit with Fe/Mg-clays. The typical restriction of clay minerals to the oldest, Noachian terrains indicates a distinctive set of processes involving water-rock interaction that was prevalent early in Mars history and may have profoundly influenced the evolution of Martian geochemical systems. Current analyses of orbital data have led to the proposition of multiple clay-formation mechanisms, varying in space and time in their relative importance. These include near-surface weathering, formation in ice-dominated near-surface groundwaters, and formation by subsurface hydrothermal fluids. Near-surface, open system formation of clays would lead to fractionation of Mars’ crustal reservoir into an altered crustal reservoir and a sedimentary reservoir, potentially involving changes in the composition of Mars’ atmosphere. In contrast, formation of clays in the subsurface by either aqueous alteration or magmatic cooling would result in comparatively little geochemical fractionation or interaction of Mars’ atmospheric, crustal, and magmatic reservoirs, with the exception of long-term sequestration of water. Formation of clays within ice would have geochemical consequences intermediate between these endmembers. We outline the future analyses of orbital data, in situ measurements acquired within clay-bearing terrains, and analyses of Mars samples that are needed to more fully elucidate the mechanisms of martian clay formation and to determine the consequences for the geochemical evolution of the planet.     

The Extinct Radionuclide Timescale of the Early Solar System

The tendency of iodine to be mobilised during secondary processing is reflected both in the presence of ¹²⁹Xe_XS in secondary minerals and in the bulk ¹²⁹Xe_XS/I ratios in meteorites. Comparison of absolute ages derived through calibration of chronometers based on ¹²⁹Xe, ⁵³Mn and ²⁶Al against the Pb-Pb system yields a plausible timescale for the early solar system. In this system, the earliest chondrule ages are most readily interpreted as representing formation after the beginning of parent body processing. This revised version was published online in June 2006 with corrections to the Cover Date.     

Transforming Dust to Planets

We review recent progress in understanding how nebular dust and gas are converted into the planets of the present-day solar system, focusing particularly on the “Grand Tack” and pebble accretion scenarios. The Grand Tack can explain the observed division of the solar system into two different isotopic “flavours”, which are found in both differentiated and undifferentiated meteorites. The isotopic chronology inferred for the development of these two “flavours” is consistent with expectations of gas-giant growth and nebular gas loss timescales. The Grand Tack naturally makes a small Mars and a depleted, dynamically-excited and compositionally mixed asteroid belt (as observed); it builds both Mars and the Earth rapidly, which is consistent with the isotopically-inferred growth timescale of the former, but not the latter. Pebble accretion can explain the rapid required growth of Jupiter and Saturn, and the number of Kuiper Belt binaries, but requires specific assumptions to explain the relatively protracted growth timescale of Earth. Pure pebble accretion cannot explain the mixing observed in the asteroid belt, the fast proto-Earth spin rate, or the tilt of Uranus. No current observation requires pebble accretion to have operated in the inner solar system, but the thermal and compositional consequences of pebble accretion have yet to be explored in detail.     

On the Isotopic Composition of Primordial Xenon in Terrestrial Planet Atmospheres

Xenon plays a crucial role in models of atmospheric evolution in which noble gases are fractionated from their initial compositions to isotopically heavier distributions by early hydrodynamic escape of primordial planetary atmospheres. With the assumption that nonradiogenic Xe isotope ratios in present-day atmospheres were generated in this way, backward modeling from these ratios through the fractionating process can in principle identify likely parental Xe compositions and thus the probable sources of noble gases in pre-escape atmospheres. Applied to Earth, this approach simultaneously establishes the presence of an atmospheric Xe component due principally to fission of extinct ²⁴⁴Pu and identifies a composition called U-Xe as primordial Xe. Pu-Xe comprises 4.65±0.30% of atmospheric ¹³⁶Xe, and 6.8±0.5% of the present abundance of ¹²⁹Xe derives from decay of extinct ¹²⁹I. U-Xe is identical to the measured composition of solar-wind Xe except for deficits of the two heaviest isotopes – an unexpected difference since the modeling otherwise points to solar wind compositions for the lighter noble gases in the primordial terrestrial atmosphere. Evidence for the presence of U-Xe is not restricted to the early Earth; modeling based on a purely meteoritic data set defines a parental component in chondrites and achondrites with the same isotopic distribution. Results of experimental efforts to measure this composition directly in meteorites are promising but not yet conclusive. U-Xe also appears as a possible base component in interstellar silicon carbide, here with superimposed excesses of ¹³⁴Xe and ¹³⁶Xe six-fold larger than those in the solar wind. These compositional differences imply mixing of U-Xe with a nucleogenetic heavy-isotope component whose relative abundance in the solar accretion disk and in pre-solar environments varied both spatially and temporally. In contrast to Earth, the U-Xe signature on Mars was apparently overwhelmed by local accretion of materials rich in either chondritic Xe or solar-wind Xe. Data currently in hand from SNC meteorites on the composition of the present atmosphere are insufficiently precise to constrain a modeling choice between these two candidates for primordial martian Xe. They likewise do not permit definitive resolution of a ²⁴⁴Pu component in the atmosphere although its presence is allowed within current measurement uncertainties. This revised version was published online in June 2006 with corrections to the Cover Date.     

The Solar Noble Gas Record in Lunar Samples and Meteorites

Lunar soil and certain meteorites contain noble gases trapped from the solar wind at various times in the past. The progress in the last decade to decipher these precious archives of solar history is reviewed. The samples appear to contain two solar noble gas components with different isotopic composition. The solar wind component resides very close to grain surfaces and its isotopic composition is identical to that of present-day solar wind. Experimental evidence seems by now overwhelming that somewhat deeper inside the grains there exists a second, isotopically heavier component. To explain the origin of this component remains a challenge, because it is much too abundant to be readily reconciled with the known present day flux of solar particles with energies above those of the solar wind. The isotopic composition of solar wind noble gases may have changed slightly over the past few Ga, but such a change is not firmly established. The upper limit of ~5% per Ga for a secular increase of the 3He/4He ratio sets stringent limits on the amount of He that may have been brought from the solar interior to the surface (cf. Bochsler, 1992). Relative abundances of He, Ne, and Ar in present-day solar wind are the same as the long term average recorded in metallic Fe grains in meteorites within error limits of some 15-20%. Xe, and to a lesser extent Kr, are enriched in the solar wind similar to elements with a first ionisation potential < 10 eV, although Kr and Xe have higher FIPs. This can be explained if the ionisation time governs the FIP effect (Geiss and Bochsler, 1986). This revised version was published online in June 2006 with corrections to the Cover Date.     

Geophysical Constraints on the Evolution of Mars

The evolution of Mars is discussed using results from the recent Mars Global Surveyor (MGS) and Mars Pathfinder missions together with results from mantle convection and thermal history models and the chemistry of Martian meteorites. The new MGS topography and gravity data and the data on the rotation of Mars from Mars Pathfinder constrain models of the present interior structure and allow estimates of present crust thickness and thickness variations. The data also allow estimates of lithosphere thickness variation and heat flow assuming that the base of the lithosphere is an isotherm. Although the interpretation is not unambiguous, it can be concluded that Mars has a substantial crust. It may be about 50 km thick on average with thickness variations of another ±50 km. Alternatively, the crust may be substantially thicker with smaller thickness variations. The former estimate of crust thickness can be shown to be in agreement with estimates of volcanic production rates from geologic mapping using data from the camera on MGS and previous missions. According to these estimates most of the crust was produced in the Noachian, roughly the first Gyr of evolution. A substantial part of the lava generated during this time apparently poured onto the surface to produce the Tharsis bulge, the largest tectonic unit in the solar system and the major volcanic center of Mars. Models of crust growth that couple crust growth to mantle convection and thermal evolution are consistent with an early 1 Gyr long phase of vigorous volcanic activity. The simplest explanation for the remnant magnetization of crustal units of mostly the southern hemisphere calls for an active dynamo in the Noachian, again consistent with thermal history calculations that predict the core to become stably stratified after some hundred Myr of convective cooling and dynamo action. The isotope record of the Martian meteorites suggest that the core formed early and rapidly within a few tens of Myr. These data also suggest that the silicate rock component of the planet was partially molten during that time. The isotope data suggest that heterogeneity resulted from core formation and early differentiation and persisted to the recent past. This is often taken as evidence against vigorous mantle convection and early plate tectonics on Mars although the latter assumption can most easily explain the early magnetic field. The physics of mantle convection suggests that there may be a few hundred km thick stagnant, near surface layer in the mantle that would have formed rapidly and may have provided the reservoirs required to explain the isotope data. The relation between the planform of mantle convection and the tectonic features on the surface is difficult to entangle. Models call for long wavelength forms of flow and possibly a few strong plumes in the very early evolution. These plumes may have dissolved with time as the core cooled and may have died off by the end of the Noachian.     

An Oxygen Isotope Mixing Model for the Accretion and Composition of Rocky Planets

The oxygen isotope systematics in planetary and nebular matter are used to constrain the types of nebular material accreted to form a planet. The basic assumption of this model is that the mean oxygen isotopic composition of a planet is determined by the weighted mean oxygen isotopic composition of nebular matter accreted by the planet. Chondrites are taken as representatives of nebular matter. The chemical composition (which determines core size, mantle oxidation state, density, moment of inertia) of a planet results from the weighted mean compositions of the accreted nebular material, once the mass fractions of the different types of accreting matter are known. Here some results for Earth, Moon, Mars, and Vesta are discussed. The model implies that loss of volatile elements, such as alkalis and halogens, occurs during accretion and early planetary differentiation (e. g., by catastrophic impacts). The possible depletion mechanisms of moderately volatile elements are discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Are There Chemical Gradients in the Inner Solar System?

The solar system is apparently stratified with regard to the contents of volatile constituents, as judged from the rocky, volatile-poor inner solar system planets and meteorites and the huge volatile-rich outer planets. However, beyond this gross structure there is no evidence for a systematic increase of the volatiles' abundances with distance from the Sun. Although meteorites show comparatively large differences in volatile element contents they also differ in many other respects, such as Mg/Si-ratios, bulk Fe and refractory element contents. These variations reflect variations in the nebular environment from which meteorites formed. The various conditions of meteorite formation cannot, however, be related in a simple way to heliocentric distances. There are also no systematic variations in the chemistry of the inner planets Mercury, Venus, Earth, Moon, Mars, and including the fourth largest asteroid Vesta, that could be interpreted as a relationship between volatility and composition. Although Mars (as judged from the composition of Martian meteorites) is more oxidized and contains more volatile elements than Earth, this trend cannot be extrapolated to the dry volatile poor Vesta (sampled by HED meteorites) in the asteroid belt. If the Earth-Mars trend reflects global inner solar system gradients then Vesta must have formed inside Earth's orbit and moved out later to its present location. The quality of Mercury and Venus composition data is not sufficient to allow reliable extrapolation to distances closer to the Sun. Recent nebula models predict small temperature gradients in the inner solar system supporting the view that no large variations in volatile element contents of inner solar system materials are expected. This revised version was published online in June 2006 with corrections to the Cover Date.