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.     

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.     

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.     

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 and Volatile Inventories of Mercury,Venus, the Moon,and Mars

We review the geochemical observations of water, \(\mbox{D}/\mbox{H}\) and volatile element abundances of the inner Solar System bodies, Mercury, Venus, the Moon, and Mars. We focus primarily on the inventories of water in these bodies, but also consider other volatiles when they can inform us about water. For Mercury, we have no data for internal water, but the reducing nature of the surface of Mercury would suggest that some hydrogen may be retained in its core. We evaluate the current knowledge and understanding of venusian water and volatiles and conclude that the venusian mantle was likely endowed with as much water as Earth of which it retains a small but non-negligible fraction. Estimates of the abundance of the Moon’s internal water vary from Earth-like to one to two orders of magnitude more depleted. Cl, K, and Zn isotope anomalies for lunar samples argue that the giant impact left a unique geochemical fingerprint on the Moon, but not the Earth. For Mars, an early magma ocean likely generated a thick crust; this combined with a lack of crustal recycling mechanisms would have led to early isolation of the Martian mantle from later delivery of water and volatiles from surface reservoirs or late accretion. The abundance estimates of Martian mantle water are similar to those of the terrestrial mantle, suggesting some similarities in the water and volatile inventories for the terrestrial planets and the Moon.     

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.     

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.     

Origin, Internal Structure and Evolution of 4 Vesta

Asteroid 4 Vesta is the only preserved intact example of a large, differentiated protoplanet like those believed to be the building blocks of terrestrial planet accretion. Vesta accreted rapidly from the solar nebula in the inner asteroid belt and likely melted due to heat released due to the decay of ²⁶Al. Analyses of meteorites from the howardite-eucrite-diogenite (HED) suite, which have been both spectroscopically and dynamically linked to Vesta, lead to a model of the asteroid with a basaltic crust that overlies a depleted peridotitic mantle and an iron core. Vesta??s crust may become more mafic with depth and might have been intruded by plutons arising from mantle melting. Constraints on the asteroid??s moments of inertia from the long-wavelength gravity field, pole position and rotation, informed by bulk composition estimates, allow tradeoffs between mantle density and core size; cores of up to half the planetary radius can be consistent with plausible mantle compositions. The asteroid??s present surface is expected to consist of widespread volcanic terrain, modified extensively by impacts that exposed the underlying crust or possibly the mantle. Hemispheric heterogeneity has been observed by poorly resolved imaging of the surface that suggests the possibility of a physiographic dichotomy as occurs on other terrestrial planets. Vesta might have had an early magma ocean but details of the early thermal structure are far from clear owing to model uncertainties and paradoxical observations from the HEDs. Petrological analysis of the eucrites coupled with thermal evolution modeling recognizes two possible mechanisms of silicate-metal differentiation leading to the formation of the basaltic achondrites: equilibrium partial melting or crystallization of residual liquid from the cooling magma ocean. A firmer understanding the plethora of complex physical and chemical processes that contribute to melting and crystallization will ultimately be required to distinguish among these possibilities. The most prominent physiographic feature on Vesta is the massive south polar basin, whose formation likely re-oriented the body axis of the asteroid??s rotation. The large impact represents the likely major mechanism of ejection of fragments that became the HEDs. Observations from the Dawn mission hold the promise of revolutionizing our understanding of 4 Vesta, and by extension, the nature of collisional, melting and differentiation processes in the nascent solar system.     

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.     

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.     

Thermal Evolution and Magnetic Field Generation in Terrestrial Planets and Satellites

Of the terrestrial planets, Earth and Mercury have self-sustained fields while Mars and Venus do not. Magnetic field data recorded at Ganymede have been interpreted as evidence of a self-generated magnetic field. The other icy Galilean satellites have magnetic fields induced in their subsurface oceans while Io and the Saturnian satellite Titan apparently are lacking magnetic fields of internal origin altogether. Parts of the lunar crust are remanently magnetized as are parts of the crust of Mars. While it is widely accepted that the magnetization of the Martian crust has been caused by an early magnetic field, for the Moon alternative explanations link the magnetization to plasma generated by large impacts. The necessary conditions for a dynamo in the terrestrial planets and satellites are the existence of an iron-rich core that is undergoing intense fluid motion. It is widely accepted that the fluid motion is caused by convection driven either by thermal buoyancy or by chemical buoyancy or by both. The chemical buoyancy is released upon the growth of an inner core. The latter requires a light alloying element in the core that is enriched in the outer core as the solid inner core grows. In most models, the light alloying element is assumed to be sulfur, but other elements such as, e.g., oxygen, silicon, and hydrogen are possible. The existence of cores in the terrestrial planets is either proven beyond reasonable doubt (Earth, Mars, and Mercury) or the case for a core is compelling as for Venus and the Moon. The Galilean satellites Io and Ganymede are likely to have cores judging from Galileo radio tracking data of the gravity fields of these satellites. The case is less clear cut for Europa. Callisto is widely taken as undifferentiated or only partially differentiated, thereby lacking an iron-rich core. Whether or not Titan has a core is not known at the present time. The terrestrial planets that do have magnetic fields either have a well-established inner core with known radius and density such as Earth or are widely agreed to have an inner core such as Mercury. The absence of an inner core in Venus, Mars, and the Moon (terrestrial bodies that lack fields) is not as well established although considered likely. The composition of the Martian core may be close to the Fe–FeS eutectic which would prevent an inner core to grow as long as the core has not cooled to temperatures around 1500 Kelvin. Venus may be on the verge of growing an inner core in which case a chemical dynamo may begin to operate in the geologically near future. The remanent magnetization of the Martian and the lunar crust is evidence for a dynamo in Mars’ and possibly the Moon’s early evolution and suggests that powerful thermally driven dynamos are possible. Both the thermally and the chemically driven dynamo require that the core is cooled at a sufficient rate by the mantle. For the thermally driven dynamo, the heat flow from the core into the mantle must by larger than the heat conducted along the core adiabat to allow a convecting core. This threshold is a few mW?m^?2 for small planets such as Mercury, Ganymede, and the Moon but can be as large as a few tens mW?m^?2 for Earth and Venus. The buoyancy for both dynamos must be sufficiently strong to overcome Ohmic dissipation. On Earth, plate tectonics and mantle convection cool the core efficiently. Stagnant lid convection on Mars and Venus are less efficient to cool the core but it is possible and has been suggested that Mars had plate tectonics in its early evolution and that Venus has experienced episodic resurfacing and mantle turnover. Both may have had profound implications for the evolution of the cores of these planets. It is even possible that inner cores started to grow in Mars and Venus but that the growth was frustrated as the mantles heated following the cessation of plate tectonics and resurfacing. The generation of Ganymede’s magnetic field is widely debated. Models range from magneto-hydrodynamic convection in which case the field will not be self-sustained to chemical and thermally-driven dynamos. The wide range of possible compositions for Ganymede’s core allows models with a completely liquid near eutectic Fe–FeS composition as well as models with Fe inner cores or cores in with iron snowfall.     

Geochemical Reservoirs and Timing of Sulfur Cycling on Mars

Sulfate-dominated sedimentary deposits are widespread on the surface of Mars, which contrasts with the rarity of carbonate deposits, and indicates surface waters with chemical features drastically different from those on Earth. While the Earth’s surface chemistry and climate are intimately tied to the carbon cycle, it is the sulfur cycle that most strongly influences the Martian geosystems. The presence of sulfate minerals observed from orbit and in-situ via surface exploration within sedimentary rocks and unconsolidated regolith traces a history of post-Noachian aqueous processes mediated by sulfur. These materials likely formed in water-limited aqueous conditions compared to environments indicated by clay minerals and localized carbonates that formed in surface and subsurface settings on early Mars. Constraining the timing of sulfur delivery to the Martian exosphere, as well as volcanogenic H₂O is therefore central, as it combines with volcanogenic sulfur to produce acidic fluids and ice. Here, we reassess and review the Martian geochemical reservoirs of sulfur from the innermost core, to the mantle, crust, and surficial sediments. The recognized occurrences and the mineralogical features of sedimentary sulfate deposits are synthesized and summarized. Existing models of formation of sedimentary sulfate are discussed and related to weathering processes and chemical conditions of surface waters. We also review existing models of sulfur content in the Martian mantle and analyze how volcanic activities may have transferred igneous sulfur into the exosphere and evaluate the mass transfers and speciation relationships between volcanic sulfur and sedimentary sulfates. The sedimentary clay-sulfate succession can be reconciled with a continuous volcanic eruption rate throughout the Noachian-Hesperian, but a process occurring around the mid-Noachian must have profoundly changed the composition of volcanic degassing. A hypothetical increase in the oxidation state or in water content of Martian lavas or a decrease in atmospheric pressure is necessary to account for such a change in composition of volcanic gases. This would allow the pre mid-Noachian volcanic gases to be dominated by water and carbon-species but late Noachian and Hesperian volcanic gases to be sulfur-rich and characterized by high SO₂ content. Interruption of early dynamo and impact ejection of the atmosphere may have decreased the atmospheric pressure during the early Noachian whereas it remains unclear how the redox state or water content of lavas could have changed. Nevertheless, volcanic emission of SO₂ rich gases since the late Noachian can explain many features of Martian sulfate-rich regolith, including the mass of sulfate and the particular chemical features (i.e. acidity) of surface waters accompanying these deposits. How SO₂ impacted on Mars’s climate, with possible short time scale global warming and long time scale cooling effects, remains controversial. However, the ancient wet and warm era on Mars seems incompatible with elevated atmospheric sulfur dioxide because conditions favorable to volcanic SO₂ degassing were most likely not in place at this time.     

Chronology of SNC meteorites

In this paper a model is presented for the geochemical evolution of Mars which is constrained by the isotope systematics of Pb, Nd, and Sr determined for SNC meteorites (SNCs). The young magmatic crystallization ages (internal or mineral ages) of SNCs may indicate that these meteorites indeed stem from Mars. Internal ages and U-Pb and Pb-Pb systematics strongly suggest that they are the result of two magmatic processes. In addition, shock metamorphism is implied from observed petrographic shock features. For ALHA 77009 a shock-age < 15 Ma is obtained which is within uncertainty identical to the independently determined cosmic ray exposure age. It is therefore plausible that shock and exposure ages are identical for all SNCs. The Rb/Sr data of all common (non-SNC) meteorites form a 4.55 Ga isochron as do the Pb-Pb data (geochron). The SNC data fall close to these two isochrons. The Sr and Pb isotopic compositions in SNCs suggest that they formed in a recent (1.3-0.15 Ga) melting event from reservoirs which had been magmatically differentiated 4.3 ± 0.2 Ga ago. In a concordia diagram (U-Pb evolution plot) the SNC data reflect recent increase of the U/Pb ratio and the same two stage magmatic history as suggested by the other isotopic systems. The oxygen isotopic composition as well as the Nd isotopic systematics strongly suggest that the SNCs stem from one common reservoir which chemically differentiated 4.3 ± 0.2 Ga ago and then formed sub-reservoirs. In contrast to common meteorites, SNCs experienced an early magmatic differentiation where the Sm/Nd, U/Pb and Rb/Sr ratios have been strongly fractionated. In the recent magmatic process (1.3-0.15 Ga ago), in which the SNCs were formed as rocks, Sm/Nd and U/Pb were fractionated, while Rb/Sr remained similar to that of the source from which the magmas originated. During these melting events, mixing of components from different sub-reservoirs might have had occurred. At least three subreservoirs are necessary to explain the isotopic variations observed in SNCs. In contrast to the isotopic evolution of the Earth, Mars conserved remnants of the primary differentiation, a fact, which places important constraints on the tectonic evolution of Mars.     

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.     

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.     

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.     

Chemistry of the solar nebula

The composition, mineralogy and texture of chondritic meteorites suggest they are relatively unaltered relicts of the condensation and accretion processes which took place in the primitive solar nebula. Chondrites thus are thought to contain a unique record of the physico-chemical conditions which prevailed at the time and place (asteroid belt) of their origin. Elemental abundance patterns are an important clue to the events and processes. Most elements can be placed in one of four groups according to their observed fractionation behavior in chondritic material: refractory, siderophile, normally depleted and strongly depleted. This grouping can be explained in terms of four events which presumably took place during cooling, condensation and accretion in the nebula. In order of inferred occurrence these are: (1) partial loss of the initial condensates rich in refractory elements at T > 1300K, (2) partial loss of metallic Fe-Ni grains, perhaps because they were magnetic, at 1000 to 700K, (3) partial remelting and outgassing of the condensate (chondrule formation) at 600 to 350K, and (4) accretion, when the P-T conditions controlled the volatile content (500 to 350K). Total gas pressure at the time and place of accretion is estimated to fall between 10^-–6 and 10^–-4 atm.Contribution No. 80, Center for Meteorite Studies.     

The internal constitutions of the inner planets and the moon

The internal structures of the moon, Mars, Venus, and Mercury are examined in the light of what is known about the constitution of the earth. The gravitational figure of the earth as obtained from orbits of artificial satellites is used to estimate the possible deviations from hydrostatic equilibrium on other planets. Observations of the orbital and rotational motion of the moon are consistent with the hypothesis that the interior of the moon supports density inhomogeneities of the same order as those supported by the earth. The available data on the moon are insufficient to determine whether or not the moon is differentiated. The orbits of Phobos and Deimos yield an adequate value for the moment of inertia of Mars. The moment of inertia and the mass are consistent with a metallic core containing about 10 per cent of the mass of Mars. The observations of the possible magnetic field of Mars would be of importance both to the understanding of planetary magnetic fields and elucidating the internal structure of that planet. Seismic investigations on the earth yield an equation of state for silicates to pressures of about 1 × 10⁶ bars. This equation of state is used in determining density variation within Mars.The surface heat flow for the earth is consistent with the hypothesis that the concentration of radioactive elements is the same as that in chondritic meteorites. The observed ratio of potassium to uranium in surface and near-surface rocks is not consonant with the chondritic hypothesis. The moon can be of chondritic composition only if it is differentiated with the radioactivity concentrated in the upper few hundred kilometers. A chondritic composition for Mars would require a differentiation in excess of that consistent with its mass and moment of inertia. It is concluded that a chondritic composition is not a satisfactory chemical model for the inner planets.     

On The 53Mn Heterogeneity In The Early Solar System

It is well established that the prolonged and thorough mixing of numerous nucleosynthetic components that constitutes the matter in the solar nebula resulted in an essential isotopic homogeneity of the solar system material. This may or may not be true for the short-lived radionuclides which were injected into or formed within the solar nebula just prior to or during solar system formation. Distinguishing between their heterogeneous or homogeneous distribution is important because the short- lived radionuclides are now widely used for the relative chronology of various objects and processes in the early solar system and as constraints for models of nucleosynthesis. The recent studies of the ⁵³Mn-⁵³Cr isotope system (half life of ⁵³Mn is 3.7 Ma) in various solar system objects have shown that the relative abundance of radiogenic ⁵³Cr is consistent with essentially homogeneous distribution of ⁵³Mn in the asteroid belt. Thus, the relative ⁵³Mn-⁵³Cr chronometer can be directly used for dating samples which originated in the asteroid belt. Importantly, however, all meteorite groups studied so far indicate a clear excess of ⁵³Cr as compared to Earth and to a lunar sample, which exhibits also a terrestrial ⁵³Cr/⁵²Cr ratio. The results from the Martian (SNC) meteorites show that their ⁵³Cr excesses are less than half of those found in the asteroid belt bodies. Thus, the characteristic ⁵³Cr/⁵²Cr ratio of Mars is intermediate between that of the Earth-Moon system and those of the other meteorites. If these ⁵³Cr variations are viewed as a function of the heliocentric distance, the radial dependence of the relative abundances of radiogenic ⁵³Cr is indicated. This observed gradient can be explained by either an early, volatility controlled, Mn/Cr fractionation within the nebula or by an initial radial heterogeneous distribution of ⁵³Mn. Although model calculations of the Mn/Cr ratios in the bulk terrestrial planets seem to be inconsistent with the volatility driven scenario, the precision of these calculations is inadequate for eliminating this possibility. In contrast, recent studies of the ⁵³Mn-⁵³Cr system in the enstatite chondrites indicate that, while their bulk Mn/Cr ratios are essentially the same as in ordinary chondrites, the ⁵³Cr excess in bulk enstatite chondrites is three times lower than that in the bulk ordinary chondrites. This difference cannot be explained by a Mn/Cr fractionation and, thus, strongly suggests that a radial heterogeneous distribution of ⁵³Mn must have existed in at least the early inner solar system. Using the observed gradient and the ⁵³Cr/⁵²Cr ratio of the bulk enstatite chondrites, their parent body(ies) formed at ∼1.4 AU or somewhat closer to the Sun. This revised version was published online in June 2006 with corrections to the Cover Date.     

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.