147Sm‐143Nd and 176Lu‐176Hf systematics of eucrite and angrite meteorites

Comparative planetary geochemistry provides insight into the origin and evolutionary paths of planetary bodies in the inner solar system. The eucrite and angrite achondrite groups are particularly interesting because they show evidence of early planetary differentiation. We present ¹⁴⁷Sm‐¹⁴³Nd and ¹⁷⁶Lu‐¹⁷⁶Hf analyses of eight noncumulate (basaltic) eucrites, two cumulate eucrites, and three angrites, which together place new constraints on the evolution and differentiation histories of the crusts of the eucrite and angrite parent bodies and their mantle mineralogies. The chemical compositions of both eucrites and angrites indicate similar evolutionary paths and petrogenetic models with formation and isolation of differentiated crustal reservoirs associated with segregation of ilmenite. We report a ¹⁴⁷Sm‐¹⁴³Nd mineral isochron age for the Moama cumulate eucrite of 4519 ± 34 Ma (MSWD = 1.3). This age indicates protracted magmatism within deep crustal layers of the eucrite parent body lasting up to about 50 Ma after the formation of the solar system. We further demonstrate that the isotopic compositions of constituent minerals are compromised by secondary processes hindering precise determination of mineral isochron ages of basaltic eucrites and angrites. We interpret the changes in geochemistry and, consequently, the erroneous ¹⁴⁷Sm‐¹⁴³Nd and ¹⁷⁶Lu‐¹⁷⁶Hf internal mineral isochron ages of basaltic eucrites and angrites as the result of metamorphic events such as impacts (effects from pressure, temperature, and peak shock duration) on the surfaces of the eucrite and angrite parent bodies.     

Hydrogen isotopic composition of the Martian mantle inferred from the newest Martian meteorite fall,Tissint

The hydrogen isotopic composition of planetary reservoirs can provide key constraints on the origin and history of water on planets. The sources of water and the hydrological evolution of Mars may be inferred from the hydrogen isotopic compositions of mineral phases in Martian meteorites, which are currently the only samples of Mars available for Earth‐based laboratory investigations. Previous studies have shown that δD values in minerals in the Martian meteorites span a large range of ?250 to +6000‰. The highest hydrogen isotope ratios likely represent a Martian atmospheric component: either interaction with a reservoir in equilibrium with the Martian atmosphere (such as crustal water), or direct incorporation of the Martian atmosphere due to shock processes. The lowest δD values may represent those of the Martian mantle, but it has also been suggested that these values may represent terrestrial contamination in Martian meteorites. Here we report the hydrogen isotopic compositions and water contents of a variety of phases (merrillites, maskelynites, olivines, and an olivine‐hosted melt inclusion) in Tissint, the latest Martian meteorite fall that was minimally exposed to the terrestrial environment. We compared traditional sample preparation techniques with anhydrous sample preparation methods, to evaluate their effects on hydrogen isotopes, and find that for severely shocked meteorites like Tissint, the traditional sample preparation techniques increase water content and alter the D/H ratios toward more terrestrial‐like values. In the anhydrously prepared Tissint sample, we see a large range of δD values, most likely resulting from a combination of processes including magmatic degassing, secondary alteration by crustal fluids, shock‐related fractionation, and implantation of Martian atmosphere. Based on these data, our best estimate of the δD value for the Martian depleted mantle is ?116 ± 94‰, which is the lowest value measured in a phase in the anhydrously prepared section of Tissint. This value is similar to that of the terrestrial upper mantle, suggesting that water on Mars and Earth was derived from similar sources. The water contents of phases in Tissint are highly variable, and have been affected by secondary processes. Considering the H₂O abundances reported here in the driest phases (most likely representing primary igneous compositions) and appropriate partition coefficients, we estimate the H₂O content of the Tissint parent magma to be ≤0.2 wt%.     

H and Cl isotope systematics of apatite in brecciated lunar meteorites Northwest Africa 4472, Northwest Africa 773, Sayh al Uhaymir 169, and Kalahari 009

We have investigated the H and Cl systematics in apatite from four brecciated lunar meteorites. In Northwest Africa (NWA) 4472, most of the apatites contain ～2000–6000 ppm H₂O with δD between ?200 and 0‰, except for one grain isolated in the matrix, which contains ～6000 ppm H₂O with δD of ～500–900‰. This low‐δD apatite contains ～2500–7500 ppm Cl associated with δ³⁷Cl of ～15–20‰, while the high‐δD grain contains ～2500 ppm Cl with δ³⁷Cl of ～7–15‰. In NWA 773, apatites in a first group contain ～700–2500 ppm H₂O with δD values averaging around ～0 ± 100‰, while apatites in a second group contain ～5500–16500 ppm H₂O with δD ～250 ± 50‰. In Sayh al Uhaymir (SaU) 169 and Kalahari (Kal) 009, apatites are similar in terms of their H₂O contents (～600–3000 ppm) and δD values (?100 to 200‰). In SaU 169, apatites contain ～6000–10,000 ppm Cl, characterized by δ³⁷Cl of ～5–12‰. Overall, most of the analyzed apatite grains have δD within the range reported for carbonaceous chondrites, similar to apatite analyzed in ancient (>3.9 Ga) lunar magmatic. One grain in NWA 4472 has H and Cl isotope compositions similar to apatite from mare basalts. With an age of 4.35 Ga, this grain could be a representative of the oldest known lunar volcanic activity. Finally, since numerous evolved clasts in NWA 773 formed through silicate liquid immiscibility, the apatite grains with extremely high H₂O contents, reaching pure hydroxylapatite composition, could provide insights into the effects of such process on the evolution of volatiles in lunar magmas.     

Carbonate abundances and isotopic compositions in chondrites

We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ¹³C ≈ 25–75‰ and δ¹⁸O ≈ 15–35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0–130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ¹⁸O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH₄ (δ¹³C ≈ ?33‰ or ?20‰ for CO‐ or CH₄‐dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ¹⁸O ≈ ?5.5‰, and δ¹³C ≈ ?31‰ or ?17‰ for CO‐ or CH₄‐dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10–40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ¹³C ≈ 65–80‰) and less altered samples (δ¹³C ≈ 30–40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic composition (δ¹⁸O ≈ ?9.25‰, and δ¹³C ≈ ?21‰ or ?8‰ for CO‐ or CH₄‐dominated systems, respectively) if the less altered CRs had higher mole fractions of CO₂ in their fluids. Semarkona and Kaba carbonates have some of the lightest C isotopic compositions of the meteorites studied here, probably because they formed at higher temperatures and/or from more CO₂‐rich fluids. The fluids responsible for the alteration of chondrites and from which the carbonates formed were almost certainly accreted as ices. By analogy with cometary ices, CO₂ and/or CO would have dominated the trapped volatile species in the ices. The chondrites studied are too oxidized for CO‐dominated fluids to have formed in their parent bodies. If CH₄ was the dominant C species in the fluids during carbonate formation, it would have to have been generated in the parent bodies from CO and/or CO₂ when oxidation of metal by water created high partial pressures of H₂. The fact that the chondrite carbonate C/H₂O mole ratios are of the order predicted for CO/CO₂‐H₂O ices that experienced temperatures of >50–100 K suggests that the chondrites formed at radial distances of <4–15 AU.     

Sulfur in presolar silicon carbide grains from asymptotic giant branch stars

We studied 14 presolar SiC mainstream grains for C‐, Si‐, and S‐isotopic compositions and S elemental abundances. Ten grains have low levels of S contamination and CI chondrite‐normalized S/Si ratios between 2 × 10^?5 and 2 × 10^?4. All grains have S‐isotopic compositions compatible within 2σ of solar values. Their mean S isotope composition deviates from solar by at most a few percent, and is consistent with values observed for the carbon star IRC+10216, believed to be a representative source star of the grains, and the interstellar medium. The isotopic data are also consistent with stellar model predictions of low‐mass asymptotic giant branch (AGB) stars. In a δ³³S versus δ³⁴S plot the data fit along a line with a slope of 1.8 ± 0.7, suggesting imprints from galactic chemical evolution. The observed S abundances are lower than expected from equilibrium condensation of CaS in solid solution with SiC under pressure and temperature conditions inferred from the abundances of more refractory elements in SiC. Calcium to S abundance ratios are generally above unity, contrary to expectations for stoichiometric CaS solution in the grains, possibly due to condensation of CaC₂ into SiC. We observed a correlation between Mg and S abundances suggesting solid solution of MgS in SiC. The low abundances of S in mainstream grains support the view that the significantly higher abundances of excess ³²S found in some Type AB SiC grains are the result of in situ decay of radioactive ³²Si from born‐again AGB stars that condensed into AB grains.     

Carbon in howardite,eucrite and diogenite basaltic achondrites

Abstract— The C contents and isotopic compositions of four eucrites, four diogenites and two howardites have been determined. Stepped heating in an O atmosphere was employed to convert selectively different carbonaceous materials to CO₂ gas at various temperatures. This technique successfully distinguishes between terrestrial contaminants and indigenous C. With the exception of the Kapoeta howardite, the howardite, eucrite, and diogenite (HED) meteorites contain ～10–30 ppm indigenous C with δ¹³C between ?29% and ?19%. Kapoeta (a regolith breccia) has an elevated C content and δ¹³C, due to the presence of ¹³C-enriched carbonate minerals (δ¹³C ～ +20%) in CM2- or CR2-like clasts. The range in δ¹³C displayed by HED samples is similar to that of other solar system basalts, such as lunar rocks and Martian meteorites but distinctly different from that of the terrestrial mantle. The diogenites have a slightly lower total C yield and higher δ¹³C than the eucrites, which is a result of degassing of trapped CO/CC₂/CO^2–₃ from the silicate lattice during metamorphism or annealing. However, three out of the four diogenites studied appear to contain a discrete component, possibly of graphitic C coating silicate grains, that is seemingly unaffected by the extended annealing period experienced by the diogenites. It is possible that this component might host the indigenous primitive Xe recently identified in diogenites.     

Survey and evaluation of eucrite bulk compositions

Abstract— The purpose of this survey is to establish reference bulk elemental abundances for the eucrites and thereby provide the basis to test core formation models as well as partial melting, fractional crystallization and magma ocean theories for the eucrite parent body. In order to evaluate bulk elemental abundances for the eucrites, 296 peer-reviewed articles, monographs, theses or books and 143 abstracts dating from 1938 to 1997 were surveyed. Of the 101 eucrites having at least one set of elemental abundance analyses reported in the literature, 20 were selected for in-depth examination. The selection criteria of our sample were based on the total number of analyses available for a given eucrite and the total number of elements for which data exist. The mean bulk elemental abundance, 1σ standard deviation, and the percent deviation were calculated for each element in a given eucrite. In order to evaluate the quality of the mean abundances, the elements were then grouped according to availability of data and percent deviations. Possible reasons for the different deviations in the different groups are briefly discussed. From the major element abundances, the normative (CIPW) composition, the molar compositions of pyroxene, olivine and plagioclase, and the bulk densities were calculated and compared to petrographic observations. The calculated norms for the noncumulates agree well with the observations while the norms for the cumulates do not. Possible reasons for this are discussed. Unfortunately, analyses of many elements are poorly represented in the literature and many bulk analyses suffer from unacceptable levels of uncertainty. Therefore, future work requires bulk elemental analyses for some of the more poorly characterized elements in eucrites, especially those of key elements used for planetary modeling.     

Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5–10% in REE (Eu = 14%), 6–13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg‐normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are ~0.6 × CI with enriched La abundance (~0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass‐dependent isotope fractionation trend. Both groups show a ~slope‐1/2 line on a three‐isotope plot with subtle negative deviation in ?¹⁷O associated with δ¹⁸O enrichment relative to δ¹⁷O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.     

Search for sulfates on the surface of Ceres

The formation of hydrated salts is an expected consequence of aqueous alteration of Main Belt objects, particularly for large, volatile‐rich protoplanets like Ceres. Sulfates, present on water‐bearing planetary bodies (e.g., Earth, Mars, and carbonaceous chondrite parent bodies) across the inner solar system, may contribute to Ceres’ UV and IR spectral signature along with phyllosilicates and carbonates. We investigate the presence and stability of hydrated sulfates under Ceres’ cryogenic, low‐pressure environment and the consequent spectral effects, using UV–Vis–IR reflectance spectroscopy. H₂O loss begins instantaneously with vacuum exposure, measured by the attenuation of spectral water absorption bands, and a phase transition from crystalline to amorphous is observed for MgSO₄·6H₂O by X‐ray powder diffraction. Long‐term (>40 h), continuous exposure of MgSO₄·nH₂O (n = 0, 6, 7) to low pressure (10^?3–10^?6 Torr) causes material decomposition and strong UV absorption below 0.5 μm. Our measurements suggest that MgSO₄·6H₂O grains (45–83 μm) dehydrate to 2% of the original 1.9 μm water band area over ~0.3 Ma at 200 K on Ceres and after ~42 Ma for 147 K. These rates, inferred from an Avrami dehydration model, preclude MgSO₄·6H₂O as a component of Ceres’ surface, although anhydrous and minimally hydrated sulfates may be present. A comparison between Ceres emissivity spectra and laboratory reflectance measurements over the infrared range (5–17 μm) suggests sulfates cannot be excluded from Ceres’ mineralogy.     

Pristinity and petrogenesis of eucrites

New petrography, mineral chemistry, and whole rock major, minor, and trace element abundance data are reported for 29 dominantly unbrecciated basaltic (noncumulate) eucrites and one cumulate eucrite. Among unbrecciated samples, several exhibit shock darkening and impact melt veins, with incomplete preservation of primary textures. There is extensive thermal metamorphism of some eucrites, consistent with prior work. A “pristinity filter” of textural information, siderophile element abundances, and Ni/Co ratios of bulk rocks is used to address whether eucrite samples preserve endogenous refractory geochemical signatures of their asteroid parent body (i.e., Vesta), or could have experienced exogenous impact contamination. Based on these criteria, Cumulus Hills 04049, Elephant Moraine 90020, Grosvenor Range 95533, Pecora Escarpment 91245, and possibly Queen Alexander Range 97053 and Northwest Africa 1923 are pristine eucrites. Eucrite major element compositions and refractory incompatible trace element abundances are minimally affected by metamorphism or impact contamination. Eucrite petrogenesis examined through the lens of these elements is consistent with partial melting of a silicate mantle that experienced prior metal–silicate equilibrium, rather than as melts associated with cumulate diogenites. In the absence of the requirement of a large-scale magma ocean to explain eucrite petrogenesis, the interior structure of Vesta could be more heterogeneous than for larger planetary bodies.     

Volatile compounds in shergottite and nakhlite meteorites

Abstract— Vacuum pyrolysis and quadrupole mass spectrometry were used to measure evolved-gas profiles and total concentrations of H₂O, CO₂, CO, SO₂, S₂, H₂S, HCl, Cl, and hydrocarbons in both exterior and interior samples of shergottites (ALHA77005, EETA79001, and Shergotty), a nakhlite (Nakhla), and eucrites (ALHA81001, EETA79004, and Pasamonte). Eucrites were analyzed as control samples to monitor effects of terrestrial weathering and contamination, relative to properties sought for the shergottite-nakhlite parent body. In contrast with eucrites, shergottites and Nakhla contain large proportions of their sulfur as oxidized sulfur compounds. Sulfate occurs in all shergottite and Nakhla samples and carbonate was confirmed in EETA79001 and Nakhla. Carbonate and sulfate abundances are inversely correlated but total chlorine abundance varies directly with fractional sulfate abundance. Most of the volatile compounds seem to be anhydrous, based on low bulk water contents in the meteorites (<0.1% H₂O), although Nakhla might contain significant water that is chemically associated with chlorine. Traces of saturated and unsaturated hydrocarbons in some samples are most likely terrestrial contaminants. The indigenous volatile compounds indicate that the shergottite-nakhlite parent body was highly oxidizing and supported aqueous geochemistry during at least part of its history.     

Magnesium oxide-iron oxide mass balance constraints and a more detailed model for the relationship between eucrites and diogenites

Abstract— According to a currently popular model for petrogenesis on the howardite, eucrite, and diogenite (HED) parent asteroid, the diogenites are not comagmatic with most eucrites but instead formed in separate orthopyroxenite-dominated plutons. This model can be tested for consistency with mass balance for MgO and FeO, assuming the overall diogenite/(diogenite + eucrite) ratio, d, of the parent asteroid is at least comparable to the average d for the eucrite + diogenite dominated howardite regolith breccias. Average mg# (=MgO/[MgO + FeO]) is much lower for eucrites, especially noncumulate eucrites, than for diogenites. Unless the diogenite parent magmas eventually produced a large proportion of low-mg# residual basalt and gabbro (RBG), the implied initial magma's mg# is vastly higher than that of any noncumulate eucrite. Starting from a source previously depleted by putative primary eucrite genesis, melt mg# can be estimated as a function of the exchange reaction K_D and degree of melting. Using several very conservative assumptions (e.g., assuming that the total [MgO + FeO] concentration is nearly the same in the nascent melt as in the residual solids), the degree of melting required to yield a melt with mg# high enough to satisfy mass balance, without implying an RBG component that accounts for >50% of all eucrites, is an implausibly high 60–80 wt%. The separate orthopyroxenitic plutons (SOP) model also seems inconsistent with the uniform density of melts across the diogenite-eucrite compositional spectrum (2.77–2.82 g/cm³), which implies that diogenitic magmas should have been as capable as eucrites of extruding to form lavas. This difficulty cannot be reduced by simply assuming that later-formed magmas were systematically both more plutonic and more MgO-rich than earlier ones, because the plutonic cumulate eucrites equilibrated with melts systematically lower in mg# than noncumulate eucrites. Conceivably, the bulk mg# of the asteroid's silicate system was increased between primary-melt eucrite genesis and SOP diogenite genesis by graphite-fueled reduction of FeO. However, the graphite oxidation process generates a huge proportion of gas, which would have enhanced the buoyancy of the nascent diogenite-parent magmas, thus exacerbating the difficulty of achieving the implied high degrees of partial melting. To avoid these difficulties but still form most eucrites as rapidly cooled extrusives, I propose the NERD (noncumulate eucrites as extruded residua of diogenites) model. In this model, the diogenites form as early cumulates from a large magma system (probably a global “magma ocean”) that yields a large proportion of eucritic melt as residuum. This residual melt zone undergoes relatively little crystallization during a period when it is episodically tapped to produce extrusions, dikes and sills of rapidly cooled noncumulate eucrites. Slight (～5–10%) porosity in the nascent eucritic crust keeps it marginally buoyant over the residual melt zone. The common thermal metamorphism of noncumulate eucrites results from baking by superjacent flows during the episodic venting of the melt zone. The NERD model's greatest advantage is that it does not require implausibly high degrees of localized melting in the mature stages of igneous evolution of the HED asteroid.     

Mechanisms for incorporation of hydrogen in and on terrestrial planetary surfaces

Storage of hydrogen atoms in or on a planetary surface can take place via several different mechanisms. If the hydrogen atom reacts to form a hydroxyl (OH) group or water molecule, an absorption band near 3 μm will be present. Many possible mechanisms for sequestering atomic hydrogen are discussed: internal hydrogen in the form of non-structural OH and H₂O in nominally-anhydrous minerals, structural OH in minerals, structural H₂O in minerals, H₂O in fluid inclusions, and OH and H₂O in glasses; bulk H₂O as either liquid water or ice; and surficial hydrogen that is either physisorbed as H₂O, chemisorbed as an H₂O surface complex, or chemically-bound as an OH group on surface terminal sites and grain boundary regions. Understanding the spectroscopic distinctions among these various phenomena is of critical importance in constraining both the evolution of planetary interiors and the cycling of water on planetary surfaces. Proper interpretation of 3-μm bands in reflectance spectra is shown to depend upon the relative contributions from surficial vs. interior hydrogen, which vary with effective surface area (i.e., the grain size and surface roughness) and the volume sampled by the spectrometer.     

The absorption and emission spectrum of the magnetic Herbig Ae star HD 190073

We determine abundances from the absorption spectrum of the magnetic Herbig Ae star HD 190073 (V1295 Aql). The observations are primarily from HARPS spectra obtained at a single epoch. We accept arguments that the presence of numerous emission lines does not vitiate a classical abundance analysis, though it likely reduces the achievable accuracy. Most abundances are closely solar, but several elements show departures of a factor of two to three, as an earlier study has also shown. We present quantitative measurements of more than 60 emission lines, peak intensities, equivalent widths, and FWHM's. The latter range from over 200 km s^–1(Hα, He D₃) down to 10–20 km s^–1(forbidden lines). Metallic emission lines have intermediate widths. We eschew modeling, and content ourselves with a presentation of the observations a successful model must explain. Low‐excitation features such as the Na I D‐lines and [O I] appear with He I D₃, suggesting proximate regions with widely differing T_e and N_e as found in the solar chromosphere. The [O I] and [Ca II] lines show sharp, violet‐shifted features. Additionally, [Fe II] lines appear tobe weakly present in emission (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Secondary‐volatiles linked metallic iron in eucrites: The dual‐origin metals of Camel Donga

The unique occurrence of abundant (~1 vol%) near‐pure‐Fe metal in the Camel Donga eucrite is more complicated than previously believed. In addition to that component of groundmass metal, scattered within the meteorite are discrete nodules of much higher kamacite abundance. We have studied the petrology and composition of two of these nodules in the form of samples we call CD2 and CD3. The nodules are ovoids 11 (CD2) to 15 (CD3) mm across, with metal, or inferred preweathering metal, abundances of 12–17 vol% (CD2 is unfortunately quite weathered). The CD3 nodule also includes at its center a 5 mm ovoid clumping (6 vol%) of F‐apatite. Both nodules are fine‐grained, so the high Fe metal and apatite contents are clearly not flukes of inadequate sampling. The metals within the nodules are distinctly Ni‐rich (0.3–0.6 wt%) compared to the pure‐Fe (Ni generally 0.01 wt%) groundmass metals. Bulk analyses of three pieces of the CD2 nodule show that trace siderophile elements Ir, Os, and Co are commensurately enriched; Au is enriched to a lesser degree. The siderophile evidence shows the nodules did not form by in situ reduction of pyroxene FeO. Moreover, the nodules do not show features such as silica‐phase enrichment or pyroxene with reduced FeO (as constrained by FeO/MgO and especially FeO/MnO) predicted by the in situ reduction model. The oxide minerals, even in groundmass samples well away from the nodules, also show little evidence of reduction. Although the nodule boundaries are generally sharp, groundmass‐metal Ni content is anti‐correlated with distance from the CD3 nodule. We infer that the nodules represent materials that originated within impactors into the Camel Donga portion of the eucrite crust, but probably were profoundly altered during later metamorphism/metasomatism. Origin of the pure‐Fe groundmass metal remains enigmatic. In situ reduction probably played an important role, and association in the same meteorite of the Fe‐nodules is probably significant. But the fluid during alteration was probably not (as previously modeled) purely S and O, of simple heat‐driven internal derivation. We conjecture a two‐stage metasomatism, as fluids passed through Camel Donga after impact heating of volatile‐rich chondritic masses (survivors of gentle accretionary impacts) within the nearby crust. First, reduction to form troilite may have been triggered by fluids rich in S₂ and CO (derived from the protonodules?), and then in a distinct later stage, fluids were (comparatively) H₂O‐rich, and thus reacted with troilite to form pure‐Fe metal along with H₂S and SO₂. The early eucrite crust was in places a dynamic fluid‐bearing environment that hosted complex chemical processes, including some that engendered significant diversity among metal+sulfide alterations.     

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.     

Evidence for high‐temperature fractionation of lithium isotopes during differentiation of the Moon

Lithium isotope and abundance data are reported for Apollo 15 and 17 mare basalts and the LaPaz low‐Ti mare basalt meteorites, along with lithium isotope data for carbonaceous, ordinary, and enstatite chondrites, and chondrules from the Allende CV3 meteorite. Apollo 15 low‐Ti mare basalts have lower Li contents and lower δ⁷Li (3.8 ± 1.2‰; all uncertainties are 2 standard deviations) than Apollo 17 high‐Ti mare basalts (δ⁷Li = 5.2 ± 1.2‰), with evolved LaPaz mare basalts having high Li contents, but similar low δ⁷Li (3.7 ± 0.5‰) to Apollo 15 mare basalts. In low‐Ti mare basalt 15555, the highest concentrations of Li occur in late‐stage tridymite (>20 ppm) and plagioclase (11 ± 3 ppm), with olivine (6.1 ± 3.8 ppm), pyroxene (4.2 ± 1.6 ppm), and ilmenite (0.8 ± 0.7 ppm) having lower Li concentrations. Values of δ⁷Li in low‐ and high‐Ti mare basalt sources broadly correlate negatively with ¹⁸O/¹⁶O and positively with ⁵⁶Fe/⁵⁴Fe (low‐Ti: δ⁷Li ≤4‰; δ⁵⁶Fe ≤0.04‰; δ¹⁸O ≥5.7‰; high‐Ti: δ⁷Li >6‰; δ⁵⁶Fe >0.18‰; δ¹⁸O <5.4‰). Lithium does not appear to have acted as a volatile element during planetary formation, with subequal Li contents in mare basalts compared with terrestrial, martian, or vestan basaltic rocks. Observed Li isotopic fractionations in mare basalts can potentially be explained through large‐degree, high‐temperature igneous differentiation of their source regions. Progressive magma ocean crystallization led to enrichment in Li and δ⁷Li in late‐stage liquids, probably as a consequence of preferential retention of ⁷Li and Li in the melt relative to crystallizing solids. Lithium isotopic fractionation has not been observed during extensive differentiation in terrestrial magmatic systems and may only be recognizable during extensive planetary magmatic differentiation under volatile‐poor conditions, as expected for the lunar magma ocean. Our new analyses of chondrites show that they have δ⁷Li ranging between ?2.5‰ and 4‰. The higher δ⁷Li in planetary basalts than in the compilation of chondrites (2.1 ± 1.3‰) demonstrates that differentiated planetary basalts are, on average, isotopically heavier than most chondrites.     

SOLAR ABUNDANCES OF THE ELEMENTS

The isotopic compositions of noble gases in the solar wind show high enrichments of light isotopes. When corrected for mass fractionation all five noble gases there can be resolved in terms of the two primitive noble gas components that have been identified in planetary solids. Reasons are presented for assigning the fractionation to a solar process that selectively enriches lighter nuclei at the surface of the Sun. When abundances of the elements at the Sun's surface are corrected for this fractionation, it is shown that atomic abundances for major elements in the bulk Sun are (in decreasing order): Fe, Ni, O, Si, S and Mg. Solar elements at about the 1% atomic abundance level include He, C, Ne, Ca and Cr. These results suggest that fusion of hydrogen is probably not the Sun's primary energy source.     

Fluids on differentiated asteroids: Evidence from phosphates in differentiated meteorites GRA 06128 and GRA 06129

Abstract– Paired meteorites Graves Nunatak 06128 and 06129 (GRA) represent an ancient cumulate lithology (4565.9 Ma ± 0.3) containing high abundances of sodic plagioclase. Textures and stable isotope compositions of GRA indicate that superimposed on the igneous lithology is a complex history of subsolidus reequilibration and low‐temperature alteration that may have extended over a period of 150 Myr. In GRA, apatite is halogen‐rich with Cl between 4.5 and 5.5 wt% and F between 0.3 and 0.9 wt%. The Cl/(Cl+F+OH) ratio of the apatite is between 0.65 and 0.82. The Cl and F are negatively correlated and are heterogeneously distributed in the apatite. Merrillite is low in halogens with substantial Na in the 6‐fold coordinated Na‐site (≈2.5%) and Mg in the smaller octahedral site. The merrillite has a negative Eu anomaly, whereas the apatite has a positive Eu anomaly. The chlorine isotope composition of the bulk GRA leachate is +1.2‰ relative to standard mean ocean chloride (SMOC). Ion microprobe chlorine isotope analyses of the apatite range between ?0.5 and +1.2‰. Textural relationships between the merrillite and apatite, and the high‐Cl content of the apatite, suggest that the merrillite is magmatic in origin, whereas the apatite is a product of the interaction between merrillite and a Cl‐rich fluid. If the replacement of merrillite by apatite occurred at approximately 800 °C, the fluid composition is f(HCl)/f(H₂O) = 0.0383 and a HCl molality of 2.13 and f(HCl)/f(HF) = 50–100. It is anticipated that the calculated f(HCl)/f(H₂O) and a HCl molality are minimum values due to assumptions made on the OH component in apatite and basing the calculations on the apatite with the lowest X_Cl. The bulk δ³⁷Cl of GRA is a >2σ outlier from chondritic meteorites and suggests that parent body processes resulted in fractionation of the Cl isotopes.     

The mineralogy,petrology, and composition of anomalous eucrite Emmaville

The Emmaville eucrite is a relatively poorly studied basaltic achondrite with an anomalous oxygen isotope signature. In this study, we report comprehensive mineralogical, petrographic, and geochemical data from Emmaville in order to understand its petrogenesis and relationship with the basaltic eucrites. Emmaville is an unusually fine‐grained, hornfelsic‐textured metabasalt with pervasive impact melt veins and mineral compositions similar to those of typical basaltic eucrites. The major and trace element bulk composition of Emmaville is also typical of a basaltic eucrite. Three separated individual lithologies were also analyzed for O isotopes; a dark gray fraction (E1), a shocked lithology (E2), and a lighter gray portion (E3). Fractions E1 and E2 shared similar O isotope compositions to the bulk sample (E‐B), whereas the lighter gray portion (E3) is slightly elevated in Δ¹⁷O and significantly elevated in δ¹⁸O compared to bulk. No evidence for any exogenous material is observed in the thin sections, coupled with the striking compositional similarity to typical basaltic eucrites, appears to preclude a simple impact‐mixing hypothesis. The O‐isotopes of Emmaville are similar to those of Bunburra Rockhole, A‐881394, and EET 92023, and thus distinct from the majority of the HEDs, despite having similarities in petrology, mineral, and bulk compositions. It would, therefore, seem plausible that all four of these samples are derived from a single HED‐like parent body that is isotopically distinct from that of the HEDs (Vesta) but similar in composition.