Volatile element signatures in the mantles of Earth,Moon, and Mars: Core formation fingerprints from Bi,Cd, In,and Sn

Volatile element concentrations in planets are controlled by many factors such as precursor material composition, core formation, differentiation, magma ocean and magmatic degassing, and late accretionary processes. To better constrain the role of core formation, we report new experiments defining the effect of temperature, and metallic S and C content on the metal-silicate partition coefficient (or D(i) metal/silicate) of the volatile siderophile elements (VSE) Bi, Cd, In, and Sn. Additionally, the effect of pressure on metal-silicate partitioning between 1 and 3 GPa, and olivine-melt partitioning at 1 GPa have been studied for Bi, Cd, In, Sn, As, Sb, and Ge. Temperature clearly causes a decrease in D(i) metal/silicate for all elements. Sulfur and C have a large influence on activity coefficients in metallic Fe liquids, with C causing a decrease in D(i) metal/silicate, and S causing an increase. Pressure has only a small effect on D(Cd), D(In), and D(Ge) metal/silicate. Depletions of Bi, Cd, In, and Sn in the terrestrial and Martian mantles are consistent with high PT core formation and metal-silicate equilibrium at the high temperatures indicated by previous studies. A late Hadean matte would influence Bi the most, due to its high D(sulfide/silicate) ~2000, but segregation of a matte would only reduce the mantle Bi content by 50%; all other less chalcophile elements (e.g., Sn, In, and Cd) would be minimally affected. The lunar depletions of highly VSE require a combination of core formation and an additional depletion mechanism—most likely the Moon-forming giant impact, or lunar magma ocean degassing.     

Large‐ion lithophile element fractionation during the early differentiation of Mars and the composition of the martian primitive mantle

Abstract— Basaltic shergottites display a systematic decrease in K/Th, K/U, and K/La ratios with increasing K content. These trends are interpreted as mixing lines between relatively young martian magmas derived from highly depleted mantle sources and an ancient large‐ion lithophile (LIL) element‐enriched crustal component. One implication of this is that a substantial fractionation of these ratios occurs during the early crustal differentiation on Mars. Isotopic evidence from SNC meteorites and compositional data from Pathfinder and orbital gamma ray spectroscopy suggest that in excess of 50% of the LIL element complement of Mars resides in the crustal reservoir. If so, the primitive mantle of Mars is significantly more volatile‐depleted (i.e., lower K/Th, K/U, K/La) than previously thought but probably (though not necessarily) still less volatile‐depleted than the primitive mantle of the Earth. The La/Th ratios of virtually all SNC meteorites are subchondritic, including those with the most severe LREE‐depletion. Extrapolation of the basaltic shergottite trend suggests that both the depleted mantle end member and the enriched crustal end member have subchondritic La/Th ratios. This is in contrast with the Earth where basalts from LIL element‐depleted sources such as MORB have superchondritic La/Th ratios, complementary to the subchondritic ratios of the continental crust. Accordingly, assuming that the refractory elements are in chondritic proportions for the Mars primitive mantle, an additional major geochemical reservoir must exist on Mars that may not yet have been sampled.     

Siderophile and chalcophile element abundances in shergottites: Implications for Martian core formation

Elemental abundances for volatile siderophile and chalcophile elements for Mars inform us about processes of accretion and core formation. Such data are few for Martian meteorites, and are often lacking in the growing number of desert finds. In this study, we employed laser ablation inductively coupled plasma–mass spectrometry (LA‐ICP‐MS) to analyze polished slabs of 15 Martian meteorites for the abundances of about 70 elements. This technique has high sensitivity, excellent precision, and is generally accurate as determined by comparisons of elements for which literature abundances are known. However, in some meteorites, the analyzed surface is not representative of the bulk composition due to the over‐ or underrepresentation of a key host mineral, e.g., phosphate for rare earth elements (REE). For other meteorites, the range of variation in bulk rastered analyses of REE is within the range of variation reported among bulk REE analyses in the literature. An unexpected benefit has been the determination of the abundances of Ir and Os with a precision and accuracy comparable to the isotope dilution technique. Overall, the speed and small sample consumption afforded by this technique makes it an important tool widely applicable to small or rare meteorites for which a polished sample was prepared. The new volatile siderophile and chalcophile element abundances have been employed to determine Ge and Sb abundances, and revise Zn, As, and Bi abundances for the Martian mantle. The new estimates of Martian mantle composition support core formation at intermediate pressures (14 ± 3 GPa) in a magma ocean on Mars.     

Chemical layering in the upper mantle of Mars: Evidence from olivine‐hosted melt inclusions in Tissint

Melting of Martian mantle, formation, and evolution of primary magma from the depleted mantle were previously modeled from experimental petrology and geochemical studies of Martian meteorites. Based on in situ major and trace element study of a range of olivine‐hosted melt inclusions in various stages of crystallization of Tissint, a depleted olivine–phyric shergottite, we further constrain different stages of depletion and enrichment in the depleted mantle source of the shergottite suite. Two types of melt inclusions were petrographically recognized. Type I melt inclusions occur in the megacrystic olivine core (Fo_76‐70), while type II melt inclusions are hosted by the outer mantle of the olivine (Fo_66‐55). REE‐plot indicates type I melt inclusions, which are unique because they represent the most depleted trace element data from the parent magmas of all the depleted shergottites, are an order of magnitude depleted compared to the type II melt inclusions. The absolute REE content of type II displays parallel trend but somewhat lower value than the Tissint whole‐rock. Model calculations indicate two‐stage mantle melting events followed by enrichment through mixing with a hypothetical residual melt from solidifying magma ocean. This resulted in ~10 times enrichment of incompatible trace elements from parent magma stage to the remaining melt after 45% crystallization, simulating the whole‐rock of Tissint. We rule out any assimilation due to crustal recycling into the upper mantle, as proposed by a recent study. Rather, we propose the presence of Al, Ca, Na, P, and REE‐rich layer at the shallower upper mantle above the depleted mantle source region during the geologic evolution of Mars.     

Did 26Al and impact‐induced heating differentiate Mercury?

Numerical models dealing with the planetary scale differentiation of Mercury are presented with the short‐lived nuclide, ²⁶Al, as the major heat source along with the impact‐induced heating during the accretion of planets. These two heat sources are considered to have caused differentiation of Mars, a planet with size comparable to Mercury. The chronological records and the thermal modeling of Mars indicate an early differentiation during the initial ~1 million years (Ma) of the formation of the solar system. We theorize that in case Mercury also accreted over an identical time scale, the two heat sources could have differentiated the planets. Although unlike Mars there is no chronological record of Mercury's differentiation, the proposed mechanism is worth investigation. We demonstrate distinct viable scenarios for a wide range of planetary compositions that could have produced the internal structure of Mercury as deduced by the MESSENGER mission, with a metallic iron (Fe‐Ni‐FeS) core of radius ~2000 km and a silicate mantle thickness of ~400 km. The initial compositions were derived from the enstatite and CB (Bencubbin) chondrites that were formed in the reducing environments of the early solar system. We have also considered distinct planetary accretion scenarios to understand their influence on thermal processing. The majority of our models would require impact‐induced mantle stripping of Mercury by hit and run mechanism with a protoplanet subsequent to its differentiation in order to produce the right size of mantle. However, this can be avoided if we increase the Fe‐Ni‐FeS contents to ~71% by weight. Finally, the models presented here can be used to understand the differentiation of Mercury‐like exoplanets and the planetary embryos of Venus and Earth.     

Martian meteorites: Volatile trace elements and cluster analysis

Abstract— We report data for 15 mainly volatile trace elements (Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Sb, Se, Te, Tl, U, Zn) by radiochemical neutron activation analysis (RNAA) in whole-rock samples of five Martian meteorites that, with seven others studied earlier, complete the 12 member Martian meteorite suite. Nearly all of these elements exhibit highly variable compositional continua and are richer in the Martian suite compared with other basaltic meteorites. From cluster analysis, we find that the clustering of subtypes based on these elements is virtually identical to that based on contents of major refractory elements and mineralogic/petrographic character istics, which implies that each source region on Mars was closed to volatile transport. Martian meteorite data can be used to infer volatile element contents in that planet.     

Chemical compositions of martian basalts (shergottites): Some inferences on b; formation,mantle metasomatism,and differentiation in Mars

Abstract— Bulk chemical compositions of the shergottite basalts provide important constraints on magma genesis and mantle processes in Mars. Abundances of many major and trace elements in the shergottites covary in 2 distinct groups: Group 1 (Gl) includes mostly highly incompatible elements (e.g., La, Th), and Group 2 (G2) includes mostly moderately incompatible elements (e.g., Ti, Lu, Al, Hf). Covariations of G2 elements (not necessarily linear) are consistent with partitioning between basalt magma and orthopyroxene + olivine. This fractionation represents partial melting to form the shergottites and their crystallization; the restite minerals cannot include aluminous phase(s), phosphate, ilmenite, zircon, or sulfides. Overall, abundances of Gl elements are decoupled from those of G2. In graphing abundances of a Gl element against those of a G2 element, G1/G2 abundance ratios do not appear to be random but are restricted to 4 values. Shergottites with a given G1/G2 value need not have the same crystallization age and need not fall on a single fractionation trajectory involving compatible elements (e.g., Ti versus Fe*). These observations imply that the G1/G2 families were established before basalt formation and suggest metasomatic enrichment of their source region (major carrier of G2 elements) by a component rich in Gl elements. Group 1 elements were efficiently separated from G2 elements very early in Mars' history. Such efficient fractionation is not consistent with simple petrogenesis; it requires multiple fractionations, “complex” petrogenetic processes, or minerals with unusual geochemistry. The behavior of phosphorus in this early fractionation event is inexplicable by normal petrogenetic processes and minerals. Several explanations are possible, including significant compatibility of P in majoritic garnet and the presence of P‐bearing iron metal (or a phosphide phase) in the residual solid assemblage (carrier of G2 elements). If the latter, Mars' mantle is more oxidized now than during the ancient fractionation event.     

Melting in the martian mantle: Shergottite formation and implications for present‐day mantle convection on Mars

Abstract— Radiometric age dating of the shergottite meteorites and cratering studies of lava flows in Tharsis and Elysium both demonstrate that volcanic activity has occurred on Mars in the geologically recent past. This implies that adiabatic decompression melting and upwelling convective flow in the mantle remains important on Mars at present. I present a series of numerical simulations of mantle convection and magma generation on Mars. These models test the effects of the total radioactive heating budget and of the partitioning of radioactivity between crust and mantle on the production of magma. In these models, melting is restricted to the heads of hot mantle plumes that rise from the core‐mantle boundary, consistent with the spatially localized distribution of recent volcanism on Mars. For magma production to occur on present‐day Mars, the minimum average radioactive heating rate in the martian mantle is 1.6 times 10^?12 W/kg, which corresponds to 39% of the Wanke and Dreibus (1994) radioactivity abundance. If the mantle heating rate is lower than this, the mean mantle temperature is low, and the mantle plumes experience large amounts of cooling as they rise from the base of the mantle to the surface and are, thus, unable to melt. Models with mantle radioactive heating rates of 1.8 to 2.1 times 10 ^?12 W/kg can satisfy both the present‐day volcanic resurfacing rate on Mars and the typical melt fraction observed in the shergottites. This corresponds to 43–50% of the Wanke and Dreibus radioactivity remaining in the mantle, which is geochemically reasonable for a 50 km thick crust formed by about 10% partial melting. Plausible changes to either the assumed solidus temperature or to the assumed core‐mantle boundary temperature would require a larger amount of mantle radioactivity to permit present‐day magmatism. These heating rates are slightly higher than inferred for the nakhlite source region and significantly higher than inferred from depleted shergottites such as QUE 94201. The geophysical estimate of mantle radioactivity inferred here is a global average value, while values inferred from the martian meteorites are for particular points in the martian mantle. Evidently, the martian mantle has several isotopically distinct compositions, possibly including a radioactively enriched source that has not yet been sampled by the martian meteorites. The minimum mantle heating rate corresponds to a minimum thermal Rayleigh number of 2 times 10⁶, implying that mantle convection remains moderately vigorous on present‐day Mars. The basic convective pattern on Mars appears to have been stable for most of martian history, which has prevented the mantle flow from destroying the isotopic heterogeneity.     

The early thermal evolution of Mars

Hf‐W isotopic systematics of Martian meteorites have provided evidence for the early accretion and rapid core formation of Mars. We present the results of numerical simulations performed to study the early thermal evolution and planetary scale differentiation of Mars. The simulations are confined to the initial 50 Myr (Ma) of the formation of solar system. The accretion energy produced during the growth of Mars and the decay energy due to the short‐lived radio‐nuclides ²⁶Al, ⁶⁰Fe, and the long‐lived nuclides, ⁴⁰K, ²³⁵U, ²³⁸U, and ²³²Th are incorporated as the heat sources for the thermal evolution of Mars. During the core‐mantle differentiation of Mars, the molten metallic blobs were numerically moved using Stoke's law toward the center with descent velocity that depends on the local acceleration due to gravity. Apart from the accretion and the radioactive heat energies, the gravitational energy produced during the differentiation of Mars and the associated heat transfer is also parametrically incorporated in the present work to make an assessment of its contribution to the early thermal evolution of Mars. We conclude that the accretion energy alone cannot produce widespread melting and differentiation of Mars even with an efficient consumption of the accretion energy. This makes ²⁶Al the prime source for the heating and planetary scale differentiation of Mars. We demonstrate a rapid accretion and core‐mantle differentiation of Mars within the initial ~1.5 Myr. This is consistent with the chronological records of Martian meteorites.     

Moderately and slightly siderophile element constraints on the depth and extent of melting in early Mars

The thermal history of Mars during accretion and differentiation is important for understanding some fundamental aspects of its evolution such as crust formation, mantle geochemistry, chronology, volatile loss and interior degassing, and atmospheric development. In light of data from new Martian meteorites and exploration rovers, we have made a new estimate of Martian mantle siderophile element depletions. New high pressure and temperature metal–silicate experimental partitioning data and expressions are also available. Using these new constraints, we consider the conditions under which the Martian mantle may have equilibrated with metallic liquid. The resulting conditions that best satisfy six siderophile elements—Ni, Co, W, Mo, P, and Ga—and are consistent with the solidus and liquidus of the Martian mantle phase diagram are a pressure of 14 ± 3 GPa and temperature of 2100 ± 200 K. The Martian mantle depletions of Cr and V are also consistent with metal–silicate equilibration in this pressure and temperature range if deep mantle silicate phases are also taken into account. The results are not consistent with either metal–silicate equilibrium at the surface or at the current‐day Martian core–mantle boundary. Recent measurements and modeling have concluded that deep (～17 GPa or 1350 km) mantle melting is required to explain isotopic data for Martian meteorites and the nature of differentiation into core, mantle, and crust. This is in general agreement with our estimates of the conditions of Martian core formation based on siderophile elements that result in an intermediate depth magma ocean scenario for metal–silicate equilibrium.     

Geochemical diversity of shergottite basalts: Mixing and fractionation,and their relation to Mars surface basalts

The chemical compositions of shergottite meteorites, basaltic rocks from Mars, provide a broad view of the origins and differentiation of these Martian magmas. The shergottite basalts are subdivided based on their Al contents: high‐Al basalts (Al > 5% wt) are distinct from low‐Al basalts and olivine‐phyric basalts (both with Al < 4.5% wt). Abundance ratios of highly incompatible elements (e.g., Th, La) are comparable in all the shergottites. Abundances of less incompatible elements (e.g., Ti, Lu, Hf) in olivine‐phyric and low‐Al basalts correlate well with each other, but the element abundance ratios are not constant; this suggests mixing between components, both depleted and enriched. High‐Al shergottites deviate from these trends consistent with silicate mineral fractionation. The “depleted” component is similar to the Yamato‐980459 magma; approximately, 67% crystal fractionation of this magma would yield a melt with trace element abundances like QUE 94201. The “enriched” component is like the parent magma for NWA 1068; approximately, 30% crystal fractionation from it would yield a melt with trace element abundances like the Los Angeles shergottite. This component mixing is consistent with radiogenic isotope and oxygen fugacity data. These mixing relations are consistent with the compositions of many of the Gusev crater basalts analyzed on Mars by the Spirit rover (although with only a few elements to compare). Other Mars basalts fall off the mixing relations (e.g., Wishstone at Gusev, Gale crater rocks). Their compositions imply that basalt source areas in Mars include significant complexities that are not present in the source areas for the shergottite basalts.     

Neutron absorption constraints on the composition of 4 Vesta

Global maps of the macroscopic thermal neutron absorption cross section of Vesta's regolith by the Gamma Ray and Neutron Detector (GRaND) on board the NASA Dawn spacecraft provide constraints on the abundance and distribution of Fe, Ca, Al, Mg, and other rock‐forming elements. From a circular, polar low‐altitude mapping orbit, GRaND sampled the regolith to decimeter depths with a spatial resolution of about 300 km. At this spatial scale, the variation in neutron absorption is about seven times lower than that of the Moon. The observed variation is consistent with the range of absorption for howardite whole‐rock compositions, which further supports the connection between Vesta and the howardite, eucrite, and diogenite meteorites. We find a strong correlation between neutron absorption and the percentage of eucritic materials in howardites and polymict breccias, which enables petrologic mapping of Vesta's surface. The distribution of basaltic eucrite and diogenite determined from neutron absorption measurements is qualitatively similar to that indicated by visible and near infrared spectroscopy. The Rheasilvia basin and ejecta blanket has relatively low absorption, consistent with Mg‐rich orthopyroxene. Based on a combination of Fe and neutron absorption measurements, olivine‐rich lithologies are not detected on the spatial scales sampled by GRaND. The sensitivity of GRaND to the presence of mantle material is described and implications for the absence of an olivine signature are discussed. High absorption values found in Vesta's “dark” hemisphere, where exogenic hydrogen has accumulated, indicate that this region is richer in basaltic eucrite, representative of Vesta's ancient upper crust.     

A petrogenetic model for the origin and compositional variation of the martian basaltic meteorites

Abstract— The major element, trace element, and isotopic compositional ranges of the martian basaltic meteorite source regions have been modeled assuming that planetary differentiation resulted from crystallization of a magma ocean. The models are based on low to high pressure phase relationships estimated from experimental runs and estimates of the composition of silicate Mars from the literature. These models attempt to constrain the mechanisms by which the martian meteorites obtained their superchondritic CaO/Al₂O₃ ratios and their source regions obtained their parent/daughter (⁸⁷Rb/⁸⁶Sr, ¹⁴⁷Sm/¹⁴⁴Nd, and ¹⁷⁶Lu/¹⁷⁷Hf) ratios calculated from the initial Sr, Nd, and Hf isotopic compositions of the meteorites. High pressure experiments suggest that majoritic garnet is the liquidus phase for Mars relevant compositions at or above 12 GPa. Early crystallization of this phase from a martian magma ocean yields a liquid characterized by an elevated CaO/Al₂O₃ ratio and a high Mg#. Olivine‐pyroxene‐garnet‐dominated cumulates that crystallize subsequently will also be characterized by superchondritic CaO/Al₂O₃ ratios. Melting of these cumulates yields liquids with major element compositions that are similar to calculated parental melts of the martian meteorites. Furthermore, crystallization models demonstrate that some of these cumulates have parent/daughter ratios that are similar to those calculated for the most incompatible‐element‐depleted source region (i.e., that of the meteorite Queen Alexandra [QUE] 94201). The incompatible‐element abundances of the most depleted (QUE 94201‐like) source region have also been calculated and provide an estimate of the composition of depleted martian mantle. The incompatible‐element pattern of depleted martian mantle calculated here is very similar to the pattern estimated for depleted Earth's mantle. Melting the depleted martian mantle composition reproduces the abundances of many incompatible elements in the parental melt of QUE 94201 (e.g., Ba, Th, K, P, Hf, Zr, and heavy rare earth elements) fairly well but does not reproduce the abundances of Rb, U, Ta and light rare earth elements. The source regions for meteorites such as Shergotty are successfully modeled as mixtures of depleted martian mantle and a late stage liquid trapped in the magma ocean cumulate pile. Melting of this hybrid source yields liquids with major element abundances and incompatible‐element patterns that are very similar to the Shergotty bulk rock.     

Highly siderophile element (HSE) abundances in the mantle of Mars are due to core formation at high pressure and temperature

Highly siderophile elements (HSEs) can be used to understand accretion and core formation in differentiated bodies, due to their strong affinity for FeNi metal and sulfides. Coupling experimental studies of metal–silicate partitioning with analyses of HSE contents of Martian meteorites can thus offer important constraints on the early history of Mars. Here, we report new metal–silicate partitioning data for the PGEs and Au and Re across a wide range of pressure and temperature space, with three series designed to complement existing experimental data sets for HSE. The first series examines temperature effects for D(HSE) in two metallic liquid compositions—C‐bearing and C‐free. The second series examines temperature effects for D(Re) in FeO‐bearing silicate melts and FeNi‐rich alloys. The third series presents the first systematic study of high pressure and temperature effects for D(Au). We then combine our data with previously published partitioning data to derive predictive expressions for metal–silicate partitioning of the HSE, which are subsequently used to calculate HSE concentrations of the Martian mantle during continuous accretion of Mars. Our results show that at midmantle depths in an early magma ocean (equivalent to approximately 14 GPa, 2100 °C), the HSE contents of the silicate fraction are similar to those observed in the Martian meteorite suite. This is in concert with previous studies on moderately siderophile elements. We then consider model calculations that examine the role of melting, fractional crystallization, and sulfide saturation/undersaturation in establishing the range of HSE contents in Martian meteorites derived from melting of the postcore formation mantle. The core formation modeling indicates that the HSE contents can be established by metal–silicate equilibrium early in the history of Mars, thus obviating the need for a late veneer for HSE, and by extension volatile siderophile elements, or volatiles in general.     

Ancient geologic events on Mars revealed by zircons and apatites from the Martian regolith breccia NWA 7034

Zircons and apatites in clasts and matrix from the Martian breccia NWA 7034 are well documented, timing ancient geologic events on Mars. Furthermore, in this study, zircon trace elemental content, apatite volatile content, and apatite volatile isotopic compositions measured in situ could constrain the evolution of those geologic events. The U‐Pb dates of zircons in basalt, basaltic andesite, trachyandesite igneous clasts, and the matrix are similar (4.4 Ga) suggesting intense volcanism on ancient Mars. However, two metamict zircon grains found in the matrix have an upper intercept date of ~4465 Ma in crystalline, whereas amorphous areas have a lower intercept date of 1634 ± 93 Ma. The younger date is consistent with the date of apatites (1530 ± 65 Ma), suggesting a metamorphic event that completely reset the U‐Pb system in both the amorphous areas of zircon and all apatites. δD values in all apatites negatively correlate with water content in a two‐endmember mixing trend. The D (δD up to 2459‰) and ³⁷Cl heavy core (3.8‰) of a large apatite grain suggest a D‐, ³⁷Cl‐rich fluid during the metamorphic event ~1.6 Ga ago, consistent with the trace elements Y, Hf and Ti and P in zircons. The fluid was also therefore P‐rich. The D‐, ³⁷Cl‐poor H₂O‐rich rim (<313‰) suggests the degassing of water from the Martian Cl‐poor interior at a later time. This D‐, ³⁷Cl‐poor Martian mantle reservoir could have derived from volcanic intrusions postdating the younger metamorphic event recorded in NWA 7034.     

Determining the possible building blocks of the Earth and Mars

Abstract— To determine the possible building blocks of the Earth and Mars, 225,792,840 possible combinations of the bulk oxygen isotopic and chemical compositions of 13 chondritic groups at 5% mass increments were examined. Only a very small percentage of the combinations match the oxygen isotopic composition, the assumed bulk FeO concentration, and the assumed Fe/Al weight ratio for the Earth. Since chondrites are enriched in silicon relative to estimates of the bulk Earth, none of the combinations fall near the terrestrial magmatic fractionation trend line in Mg/Si‐Al/Si space. More combinations match the oxygen isotopic composition and the assumed bulk FeO concentration for Mars. These combinations fall near the trend for shergottite meteorites in Mg/Si‐Al/Si space. One explanation for the difficulty in forming Earth out of known chondrites is that the Earth may be composed predominately of material that did not survive to the present day as meteorites. Another explanation could be that significant amounts of silicon are sequestered in the core and/or lower mantle of the Earth.     

Volatile element chemistry during metamorphism of ordinary chondritic material and some of its implications for the composition of asteroids

We used chemical equilibrium calculations to model thermal metamorphism of ordinary chondritic material as a function of temperature, pressure, and trace element abundance and use our results to discuss volatile mobilization during thermal metamorphism of ordinary chondrite parent bodies. We compiled trace element abundances in H-, L-, and LL-chondrites for the elements Ag, As, Au, Bi, Br, Cd, Cs, Cu, Ga, Ge, I, In, Pb, Rb, Sb, Se, Sn, Te, Tl, and Zn, and identified abundance trends as a function of petrographic type within each class. We calculated volatility sequences for the trace elements in ordinary chondritic material, which differ significantly from the solar nebula volatility sequence. Our results are consistent with open-system thermal metamorphism. Abundance patterns of Ag and Zn remain difficult to explain.     

Extinct isotope heterogeneities in the mantles of Earth and Mars: Implications for mantle stirring rates

Heterogeneities in terrestrial samples for ¹⁸²W/¹⁸³W and ¹⁴²Nd/¹⁴⁴Nd are only preserved in Hadean and Archean rocks while heterogeneities in ¹²⁹Xe/¹³⁰Xe and ¹³⁶Xe/¹³⁰Xe persist to very young mantle‐derived rocks. In contrast, meteorites from Mars show that the Martian mantle preserves heterogeneities in ¹⁸²W/¹⁸³W and ¹⁴²Nd/¹⁴⁴Nd up to the present. As a consequence of the probable “deep magma ocean” core formation process, we assume that the Earth and Mars both had a very early two‐mantle‐reservoir structure with different initial extinct nuclide isotopic compositions (different ¹⁸²W/¹⁸³W, ¹⁴²Nd/¹⁴⁴Nd, ¹²⁹Xe/¹³⁰Xe, ¹³⁶Xe/¹³⁰Xe ratios). Based on this assumption, we developed a simple stochastic model to trace the evolution of a mantle with two initially distinct layers for the extinct isotopes and its development into a heterogeneous mantle by convective mixing and stretching of these two layers. Using the extinct isotope system ¹⁸²Hf‐¹⁸²W, we find that the mantles of Earth and Mars exhibit substantially different mixing or stirring rates. This is consistent with Mars having cooled faster than the Earth due to its smaller size, resulting in less efficient mantle mixing for Mars. Moreover, the mantle stirring rate obtained for Earth using ¹⁸²Hf‐¹⁸²W is consistent with the mantle stirring rate of ~500 Myr constrained by the long‐lived isotope system, ⁸⁷Rb‐⁸⁷Sr and ¹⁴⁷Sm‐¹⁴³Nd. The apparent absence of ¹⁸²W/¹⁸³W isotopic heterogeneity in modern terrestrial rocks is attributed to very active mantle stirring which reduced the ¹⁸²W/¹⁸³W isotopic heterogeneity to a relatively small scale (~83 m for a mantle stirring rate of 500 Myr) compared to the common sampling scale of terrestrial basalts (~30 or 100 km). Our results also support the “deep magma ocean” core formation model as being applicable to both Mars and Earth.     

Heterogeneous distribution of H2O in the Martian interior: Implications for the abundance of H2O in depleted and enriched mantle sources

We conducted a petrologic study of apatite within 12 Martian meteorites, including 11 shergottites and one basaltic regolith breccia. These data were combined with previously published data to gain a better understanding of the abundance and distribution of volatiles in the Martian interior. Apatites in individual Martian meteorites span a wide range of compositions, indicating they did not form by equilibrium crystallization. In fact, the intrasample variation in apatite is best described by either fractional crystallization or crustal contamination with a Cl‐rich crustal component. We determined that most Martian meteorites investigated here have been affected by crustal contamination and hence cannot be used to estimate volatile abundances of the Martian mantle. Using the subset of samples that did not exhibit crustal contamination, we determined that the enriched shergottite source has 36–73 ppm H₂O and the depleted source has 14–23 ppm H₂O. This result is consistent with other observed geochemical differences between enriched and depleted shergottites and supports the idea that there are at least two geochemically distinct reservoirs in the Martian mantle. We also estimated the H₂O, Cl, and F content of the Martian crust using known crust‐mantle distributions for incompatible lithophile elements. We determined that the bulk Martian crust has ~1410 ppm H₂O, 450 ppm Cl, and 106 ppm F, and Cl and H₂O are preferentially distributed toward the Martian surface. The estimate of crustal H₂O results in a global equivalent surface layer (GEL) of ~229 m, which can account for at least some of the surface features on Mars attributed to flowing water and may be sufficient to support the past presence of a shallow sea on Mars' surface.     

Constraints on the water,chlorine, and fluorine content of the Martian mantle

Previous estimates of the volatile contents of Martian basalts, and hence their source regions, ranged from nearly volatile‐free through estimates similar to those found in terrestrial subduction zones. Here, we use the bulk chemistry of Martian meteorites, along with Martian apatite and amphibole chemistry, to constrain the volatile contents of the Martian interior. Our estimates show that the volatile content of the source region for the Martian meteorites is similar to the terrestrial Mid‐Ocean‐Ridge Mantle source. Chlorine is enriched compared with the depleted terrestrial mantle but is similar to the terrestrial enriched source region; fluorine is similar to the terrestrial primitive mantle; and water is consistent with the terrestrial mantle. Our results show that Martian magmas were not volatile saturated; had water/chlorine and water/fluorine ratios ~0.4–18; and are most similar, in terms of volatiles, to terrestrial MORBs. Presumably, there are variations in volatile content in the Martian interior as suggested by apatite compositions, but more bulk chemical data, especially for fluorine and water, are required to investigate these variations. Finally, the Noachian Martian interior, as exemplified by surface basalts and NWA 7034, may have had higher volatile contents.