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.     

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.     

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.     

Stable Isotope Ratios as a Biomarker on Mars

As both Earth and Mars have had similar environmental conditions at least for some extended time early in their history (Jakosky and Phillips in Nature 412:237–244, 2001), the intriguing question arises whether life originated and evolved on Mars as it did on Earth (McKay and Stoker in Rev. Geophys. 27:189–214, 1989). Conceivably, early autotrophic life on Mars, like early life on Earth, used irreversible enzymatically enhanced metabolic processes that would have fractionated stable isotopes of the elements C, N, S, and Fe. Several important assumptions are made when such isotope fractionations are used as a biomarker. The purpose of this article is two-fold: (1) to discuss these assumptions for the case of carbon and to summarize new insights in abiologic reactions, and (2) to discuss the use of other stable isotope systems as a potential biomarker. It is concluded that isotopic biomarker studies on Mars will encounter several important obstacles. In the case of carbon isotopes, the most important obstacle is the absence of a contemporary abiologic carbon reservoir (such as carbonate deposits on Earth) to act as isotopic standard. The presence of a contemporary abiologic sulfate reservoir (evaporite deposits) suggests that sulfur isotopes can be used as a potential biomarker for sulfate-reducing bacteria. The best approach for tracing ancient life on Mars will be to combine several biomarker approaches; to search for complexity, and to combine small-scale isotopic variations with chemical, mineralogical, and morphological observations. An example of such a study can be a layer-specific correlation between δ ¹³C and δ ³⁴S within an ancient Martian evaporite, which morphologically resembles the typical setting of a shallow marine microbial mat.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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

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

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.     

Crustal S-Wave Velocity from Apparent Incidence Angles: A Case Study in Preparation for InSight

Retrieval of crustal structure and thickness of Mars is among the main goals of InSight. Here we investigate which constraints on the crust at the landing site can be provided by apparent P-wave incidence angles derived from P-receiver functions. We consider receiver functions for six different Mars models, calculated from synthetic seismograms generated via Instaseis from the Green’s function databases of the Marsquake Service, in detail. To allow for a larger range of crustal thicknesses and structures, we additionally analyze data from five broad-band stations across Central Europe. We find that the likely usable epicentral distance range for P-wave receiver functions on Mars lies between \(35^{\circ}\) and the core shadow, and can be extended to more than \(150^{\circ}\) by also using the PP-phase. Comparison to models for the spatial distribution of Martian seismicity indicates that sufficient seismicity should occur within the P-wave distance range around InSight within the nominal mission duration to allow for the application of our method. Apparent P-wave incidence angles are derived from the amplitudes of vertical and radial receiver functions at the P-wave onset within a range of period bands, up to 120 s. The apparent incidence angles are directly related to apparent S-wave velocities, which are inverted for the subsurface S-wave velocity structure via a grid search. The veracity of the forward calculated receiver functions and apparent S-wave velocities is ensured by benchmarking various algorithms against the Instaseis synthetics. Results indicate that apparent S-wave velocity curves provide valuable constraints on crustal thickness and structure, even without any additional constraints, and considering the location uncertainty and limited data quantity of InSight. S-wave velocities in the upper half of the crust are constrained best, but if reliable measurements at long periods are available, the curves also provide constraints down to the uppermost mantle. Besides, it is demonstrated that the apparent velocity curves can differentiate between crustal velocity models that are indistinguishable by other methods.