The formation of rims on calcium‐aluminum‐rich inclusions: Step I—Flash heating

Abstract— Wark‐Lovering rims of six calcium‐aluminum‐rich inclusions (CAIs) representing the main CAI types and groups in Allende, Efremovka and Vigarano were microsurgically separated and analysed by neutron activation analysis (NAA). All the rims have similar ～4x enrichments, relative to the interiors, of highly refractory lithophile and siderophile elements. The NAA results are confirmed by ion microprobe and scanning electron microscope (SEM) analyses of rim perovskites and rim metal grains. Less refractory Eu, Yb, V, Sr, Ca and Ni are less enriched in the rims. The refractory element patterns in the rims parallel the patterns in the outer parts of the CAIs. In particular, the rims on type B1 CAIs have the igneously fractionated rare earth element (REE) pattern of the melilite mantle below the rim and not the REE pattern of the bulk CAI, proving that the refractory elements in the rims were derived from the outer mantle and were not condensates onto the CAIs. The refractory elements were enriched in an Al₂O₃‐rich residue <50 μm thick after the most volatile ～80% of the outermost 200 μm of each CAI had been volatilized, including much Mg, Si and Ca. Some volatilization occurred below the rim, and created refractory partial melts that crystallized hibonite and gehlenitic melilite. The required “flash heating” probably exceeded 2000 °C, but for only a few seconds, in order to melt only the outer CAI and to unselectively volatilize slow‐diffusing O isotopes which show no mass fractionation in the rim. The volatilization did, however, produce “heavy” mass‐fractionated Mg in rims. In some CAIs this was later obscured when “normal” Mg diffused in from accreted olivine grains at relatively high temperature (not the lower temperature meteorite metamorphism) and created the ～50 μm set of monomineralic rim layers of pyroxene, melilite and spinel.     

Chemical and isotopic constraints on the formation and crystallization of SA-1, a basaltic Allende plagioclase-olivine inclusion

Abstract— SA-1, an unusual basaltic plagioclase-olivine inclusion (POI) in Allende, has concentric textural and mineralogic zones, a fine-grained, 100μm outer border and a coarse-grained interior with subophitic texture. Fassaite, diopside and olivine from the exterior border and interior of SA-1 have uniform intrinsic mass fractionation with isotopically heavy Mg (F_Mg = 3.6 ± 1.8‰/amu). In contrast, spinels from the spinel-rich regions adjacent to the fine-grained border have normal Mg isotopic composition (F_Mg = 0.1 ± 1.5‰/amu). The cores of large calcic (An_90,99) plagioclase have no excess ²⁶Mg, corresponding to ²⁶Mg*/ ²⁷Al < 3.7 × 10^?6. The Mg isotopic heterogeneity in SA-1 requires initial cooling rates of spinel-rich regions adjacent to the fine-grained border to be greater than ～75 °C/hr. In contrast, the subophitic texture of the interior suggests cooling rates of 5–20 °C/ hr. The minerals in SA-1 exhibit a wide range of REE abundances. Lanthanum concentrations vary from 1 × chondritic (ch) in early crystallizing diopside to 100 × ch in late crystallizing fassaite. Nepheline has 18–20 × ch LREE and 11–25 × ch HREE and iron-rich mesostasis is highly enriched in the REE with 270–400 × ch LREE and 230–280 × ch HREE. The complementary REE patterns of clinopyroxene and plagioclase and the enrichment of incompatible trace elements in the mesostasis and late crystallizing phases is consistent with closed system crystallization. The REE data for nepheline and the iron-rich mesostasis indicate these phases are in equilibrium and that nepheline crystallized from a melt. Influx of alkalies, minor Fe and halogens must have occurred during the last stages of crystallization or the inclusion must have been partially molten during Na influx as both anorthite (An₉₉) and nepheline are present in this inclusion. The preservation of isotopic heterogeneity in an inclusion that crystallized from a melt implies that melting was incomplete, allowing for survival of the relict spinels. The major and trace element abundances in SA-1 are inconsistent with formation as a mixture of nebular materials and suggest that SA-1 contains a chemically fractionated component produced by igneous differentiation.     

Trace element studies of silicate‐rich inclusions in the Guin (UNGR) and Kodaikanal (IIE) iron meteorites

Abstract— A devitrified glass inclusion from the Guin (UNGR) iron consists of cryptocrystalline feldspars, pyroxenes, and silica and is rich in SiO₂, Al₂O₃, and Na₂O. It contains a rutile grain and is in contact with a large Cl apatite. The latter is very rich in rare earth elements (REEs) (～80 × CI), which display a flat abundance pattern, except for Eu and Yb, which are underabundant. The devitrified glass is very poor in REEs (<0.1 × CI), except for Eu and Yb, which have positive abundance anomalies. Devitrified glass and Cl apatite are out of chemical equilibrium and their complementary REE patterns indicate a genesis via condensation under reducing conditions. Inclusion 1 in the Kodaikanal (IIE) iron consists of glass only, whereas inclusion 2 consists of clinopyroxene, which is partly overgrown by low‐Ca pyroxene, and apatite embedded in devitrified glass. All minerals are euhedral or have skeletal habits indicating crystallization from the liquid precursor of the glass. Pyroxenes and the apatite are rich in trace elements, indicating crystallization from a liquid that had 10–50 × CI abundances of REEs and refractory lithophile elements (RLEs). The co‐existing glass is poor in REEs (～0.1–1 × CI) and, consequently, a liquid of such chemical composition cannot have crystallized the phenocrysts. Glasses have variable chemical compositions but are rich in SiO₂, Al₂O₃, Na₂O, and K₂O as well as in HFSEs, Be, B, and Rb. The REE abundance patterns are mostly flat, except for the glass‐only inclusion, which has heavy rare earth elements (HREEs) > light rare earth elements (LREEs) and deficits in Eu and Yb—an ultrarefractory pattern. The genetic models suggested so far cannot explain what is observed and, consequently, we offer a new model for silicate inclusion formation in IIE and related irons. Nebular processes and a relationship with E meteorites (Guin) or Ca‐Al‐rich inclusions (CAIs) (Kodaikanal) are indicated. A sequence of condensation (CaS, TiN or refractory pyroxene‐rich liquids) and vapor‐solid elemental exchange can be identified that took place beginning under reducing and ending at oxidizing conditions (phosphate, rutile formation, alkali and Fe²⁺ metasomatism, metasomatic loss of REEs from glass).     

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.     

Nonporphyritic chondrules from equilibrated Rumuruti and ordinary chondrites: Chemical evidence of secondary processing

Abstract– Nineteen nonporphyritic pyroxene and pyroxene/olivine chondrules, chondrule fragments, and irregular objects were studied from two equilibrated chondrites, the ordinary (L/LL5) Knyahinya chondrite and the Rumuruti type (R4) Ouzina chondrite. Major element contents for almost all objects in the chondrites are disturbed from their chondritic ratios, most probably during metamorphic re‐equilibration. However, the volatile elements (Na₂O + K₂O) in Ouzina scatter around the CI line, probably the result of being generated and/or processed in different environments as compared with those for Knyahinya. All studied objects from Knyahinya and Ouzina possess systematically fractionated trace element abundances. Depletion of LREE with respect to HREE and ultra‐refractory HFSE documents variable degrees of LREE transport into an external mineral sink and restricted mobility of most of the HREE and HFSE. Moderately volatile elements preserve volatility‐controlled abundances. Strongly fractionated Rb/Cs ratios (up to 10× CI) in all studied objects suggest restricted mobility of the large Cs ion. All studied objects sampled and preserved Y and Ho in solar proportions, a feature that they share with the nonporphyritic chondrules of unequilibrated ordinary chondrites.     

REE abundances in the matrix of the Allende (CV) meteorite: Implications for matrix origin

Abstract— The trace element distributions in the matrix of primitive chondrites were examined using four least‐contaminated matrix specimens from the polished sections of the Allende (CV) meteorite. Analysis of rare earth element (REE), Ba, Sr, Rb, and K abundances by isotope dilution mass spectrometry revealed that the elemental abundances of lithophile elements except for alkali metals (K, Rb) in the specimens of the Allende matrix studied here are nearly CI (carbonaceous Orgueil) chondritic (～1 × CI). Compared to refractory elements, all the matrix samples exhibited systematic depletion of the moderately volatile elements K and Rb (0.1–0.5 × CI). We suggest that the matrix precursor material did not carry significant amounts of alkali metals or that the alkalis were removed from the matrix precursor material during the parent body process and/or before matrix formation and accretion. The matrix specimens displayed slightly fractionated REE abundance patterns with positive Ce anomalies (CI‐normalized La/Yb ratio = 1.32–1.65; Ce/Ce* = 1.16–1.28; Eu/Eu* = 0.98–1.10). The REE features of the Allende matrix do not indicate a direct relationship with chondrules or calcium‐aluminum‐rich inclusions (CAIs), which in turn suggests that the matrix was not formed from materials produced by the breakage and disaggregation of the chondrules or CAIs. Therefore, we infer that the Allende matrix retains the REE features acquired during the condensation process in the nebula gas.     

Chondrule trace element geochemistry at the mineral scale

Abstract– We report trace element analyses from mineral phases in chondrules from carbonaceous chondrites (Vigarano, Renazzo, and Acfer 187), carried out by laser ablation inductively coupled plasma‐mass spectrometry. Results are similar in all three meteorites. Mesostasis has rare earth element (REE) concentrations of 10–20 × CI. Low‐Ca pyroxene has light REE (LREE) concentrations near 0.1 × CI and heavy REE (HREE) near 1 × CI, respectively. Olivine has HREE concentrations at 0.1–1 × CI and LREE around 10^?2 × CI. The coarsest olivine crystals tend to have the most fractionated REE patterns, indicative of equilibrium partitioning. Low‐Ca pyroxene in the most pyroxene‐rich chondrules tends to have the lowest REE concentrations. Type I chondrules seem to have undergone a significant degree of batch crystallization (as opposed to fractional crystallization), which requires cooling rates slower than 1–100 K h^?1. This would fill the gap between igneous calcium‐aluminum‐rich inclusions (CAIs) and type II chondrules. The anticorrelation between REE abundances and pyroxene mode may be understood as due to dilution by addition of silica to the chondrule melt, as in the gas‐melt interaction scenario of Libourel et al. (2006). The rapid cooling rate (of the order of 1000 K h^?1) which seems recorded by low‐Ca pyroxene, contrasted with the more diverse record of olivine, may point to a nonlinear cooling history or suggest that formation of pyroxene‐rich chondrule margins was an event distinct from the crystallization of the interior.     

Fractionation of refractory siderophile elements in metal from the Rose City meteorite

Abstract— An ～4 × 9 × 12-mm concentration of metal (dubbed RC1) situated between silicate melt and a relict chondritic clast in the Rose City H5 impact-melt breccia is compositionally heterogeneous. Approximately 65 wt% of RC1 is enriched in the refractory siderophile elements, Os and Ir, by 30–40% relative to bulk H chondrite metal; ～20 wt% is depleted in these elements by 31–35%; and 15 wt% is depleted by a considerably greater amount (75%). Common and volatile siderophile elements are essentially unfractionated in all three regions; W is fractionated to only a moderate degree. The compositions of the different regions of RC1 are similar to those of previously analyzed metal nodules and veins in shocked but unmelted ordinary chondrites. All of these objects probably formed by a complex process involving vaporization of chondritic material, rapidly followed by oxidation of W to form volatile oxides, fractional condensation of refractory siderophile elements, transport of the residual vapor (containing common and volatile siderophile elements as well as W oxide) and condensation of this vapor in fractures and voids or on metallic liquid substrates. The common occurrence of vugs in shock-heated chondrites and the pervasiveness of vaporization effects recorded in metal masses and veins underscores the important role of superheating in the formation of impact breccias.     

Light rare earth element enrichments in ureilites: A detailed ion microprobe study

Abstract— This paper explores the possible origin of the light rare earth element (LREE) enrichments observed in some ureilites, a question that has both petrogenetic and chronologic implications for this group of achondritic meteorites. Rare earth element and other selected elemental abundances were measured in situ in 14 thin sections representing 11 different ureilites. The spatial microdistributions of REEs in C‐rich matrix areas of the three ureilites with the most striking V‐shaped whole‐rock REE patterns (Kenna, Goalpara, and Novo Urei) were investigated using the ion imaging capability of the ion microprobe. All olivines and clinopyroxenes measured have LREE‐depleted patterns with little variation in REE abundances, despite large differences in their major element compositions from ureilite to ureilite. Furthermore, we searched for but did not find any minor mineral phases that carry LREEs. The only exception is one Ti‐rich area (～20μm) in Lewis Cliff (LEW) 85400 with a major element composition similar to that of titanite; REE abundances in this area are high, ranging from La ? 400 × CI to Lu ? 40 × CI. In contrast, all ion microprobe analyses of C‐rich matrix in Kenna, Goalpara, and Novo Urei revealed large LREE enrichments. In addition, C‐rich matrix areas in the three polymict ureilites, Elephant Moraine (EET) 83309, EET 87720, and North Haig, which have less pronounced V‐shaped whole‐rock REE patterns, show smaller but distinct LREE‐enrichments. The C‐rich matrix in Antarctic ureilites tends to have much lower LREE concentrations than the matrix in non‐Antarctic ureilites. There is no obvious association of the LREEs with other major or minor elements in the C‐rich areas. Ion images further show that the LREE enrichments are homogeneously distributed on a microscale in most C‐rich matrix areas of Kenna, Goalpara, and Novo Urei. These observations suggest that the LREEs in ureilites most probably are absorbed on the surface of fine‐grained amorphous graphite in the C‐rich matrix. It is unlikely that the LREE enrichments are due to shock melts or are the products of metasomatism on the ureilite parent body. We favor LREE introduction by terrestrial contamination.     

The igneous crystallization history of an ancient Martian meteorite from rare earth element microdistributions

Abstract— Rare earth element (REE) and other selected trace and minor element concentrations were measured in individual grains of orthopyroxene, feldspathic glass (of plagioclase composition) and merrillite of the ALH 84001 Martian meteorite. Unlike in other Martian meteorites, phosphate is not the main REE carrier in ALH 84001. The REE pattern of ALH 84001 bulk rock is dependent on the modal abundances of three REE-bearing phases, namely, orthopyroxene, which contains most of the heavy rare earth elements (HREEs); feldspathic glass, which dominates the Eu abundances; and merrillite, which contains the majority of the light rare earth elements (LREEs). Variations in the REE abundances previously observed in different splits of ALH 84001 can easily be explained in terms of small variations in the modal abundances of these three minerals without the need to invoke extensive redistribution of LREEs. At least some orthopyroxenes (i.e., those away from contacts with feldspathic glass) in ALH 84001 appear to have preserved their original REE zonation from igneous fractionation. An estimate of the ALH 84001 parent magma composition from that of the unaltered orthopyroxene “core” (i.e., zoned orthopyroxene with the lowest REE abundances) indicates that it is LREE depleted. This implies that the Martian mantle was already partly depleted within ～100 Ma of solar system formation, which is consistent with rapid accretion and differentiation of Mars. Although equilibration and exchange of REEs between phases (in particular, transport of LREEs into the interstitial phases, feldspathic glass and merrillite) cannot be ruled out, our data suggest that the LREE enrichment in melts “in equilibrium” with these interstitial phases is most likely the result of late-stage infiltration of the cumulate pile by a LREE-enriched melt.     

The condensation and fractionation of refractory lithophile elements

It has long been recognized that Cr, Mg, and Si are fractionated in chondritic material along with, but to a much lesser extent than, a large group of more refractory elements. Reasoning that this might imply some unique distribution at the time of fractionation, the patterns have been reexamined. It now appears as if two distinct fractionation patterns can be resolved: one involving ordinary and enstatite chondrites and the other involving carbonaceous chondrites, the Earth, the Moon, and the eucrite parent body. Significantly, the two trends inevitably intersect at C1 composition. Ordinary and enstatite chondrites appear to have evolved from C1 composition via the removal of about 40 and 56% of a high-temperature condensate. Another high-temperature condensate, with a distinctly different composition, appears to be enriched in the carbonaceous chondrites, the Moon, and possibly the Earth, but depleted in the eucrite parent body. The compositions of these two components are constrained to fall on the appropriate mixing lines. These lines intersect the condensation path at two points, one where Mg₂SiO₄ has just begun to condense (～20%) and a second where Mg₂SiO₄ was almost completely condensed (～90%). This represents about an 80° temperature difference. But it is within this range that the largest fraction of planetary matter (Mg, Si, and Fe) condenses. Conceivably the relatively sudden appearance of large amounts of condensed material is in some way related to the fractionation process, although the exact relationship cannot be specified.     

Geochemistry and neodymium-strontium isotope signature of tektite-like objects from Siberia (urengoites,South-Ural glass)

Abstract— We report Sr-Nd isotope parameters, rare earth element (REE), and major element data for isolated findings of tektite-like objects from western Siberia (urengoites, South-Ural glass), as well as for two indochinites. The latter were recovered in Vietnam and their overall geochemical characteristics equal those of other tektites from the indochinite subgroup of the Australasian strewn field. The three urengoites (～24 Ma) are extremely silica-rich (89 to 96 wt% SiC₂), and their REE abundances vary between 45 and 76 ppm. With La_N/Yb_N ranging from 7.6 to 10.4 and Eu_N/EU* between 0.69 and 0.75, their REE distribution patterns match that of average upper crust. The urengoites have present-day ?_Sr of +155 to +174 and ?_Nd ranging from ?18 to ?23. Their model ages in million years are: T^SruR = 1200 up to 4060 and T^NdcHUR = 1570 up to 2070. Data points for the urengoites plot colinearly in the Rb-Sr evolution diagram. The age corresponding to the slope is 183 ± 30 Ma (2s?), which is indistinguishable from the intercept age of 211 Ma in the T^Sr_UR vs. l/f_Rb diagram. Rubidium-strontium and Sm-Nd systematics of the urengoites indicate a heterogeneous precursor material, derived from Paleoproterozoic continental crust, which underwent Rb/Sr fractionation and partial Sr isotope homogenization in Jurassic times. Any relation between the urengoites and the Haughton impact crater, having within 2s? errors an identical age, can be excluded on the basis of isotope relationships and geochemical data. The only known South-Ural glass (～6.2 Ma) is characterized by intermediate SiO₂ (65 wt%), high Al₂O₃ (14 wt%) and CaO (12 wt%), and low FeO_TOT (0.4 wt%) contents. This unique tektite-like object contains 110 ppm REE displaying a steeply negative C1 normalized distribution with La_N/Yb_N of 17, and Eu_N/Eu¹ of 0.71. The Rb abundance (10 ppm) and Rb/Sr ratio are low, and combined with a “crustal” ⁸⁷Sr/⁸⁶Sr ratio of 0.722, yielding an unrealistic T^SruR age of 2.5 Ga. The Rb-Sr systematics imply a rather recent parent/daughter element decoupling. The T^NdCHUR age of the South-Ural glass is ～1690 Ma. Geochemical data suggest that urengoites and the South-Ural glass belong to two discrete groups of tektites, whose source craters remain to be discovered.     

Watson: A new link in the HE iron chain

Abstract— Watson, which was found in 1972 in South Australia, contains the largest single silicate rock mass seen in any known iron meteorite. A comprehensive study has been completed on this unusual meteorite: petrography, metallography, analyses of the silicate inclusion (whole rock chemical analysis, INAA, RNAA, noble gases, and oxygen isotope analysis) and mineral compositions (by electron microprobe and ion microprobe). The whole rock has a composition of an H-chondrite minus the normal H-group metal and troilite content. The oxygen isotope composition is that of the silicates in the HE iron meteorites and lies along an oxygen isotope fractionation line with the H-group chondrites. Trace elements in the metal confirm Watson is a new HE iron. Whole rock Watson silicate shows an enrichment in K and P (each ～2X H-chondrites). The silicate inclusion has a highly equilibrated igneous (peridotite-like) texture with olivine largely poikilitic within low-Ca pyroxene: olivine (Fa₂₀), opx (Fs₁₇Wo₃), capx (Fs₉Wo₄₁) (with very fine exsolution lamellae), antiperthite feldspar (An_1–Or₅) with <1 μm exsolution lamellae (An_1–3Or_>40), shocked feldspar with altered stoichiometry, minor whitlockite (also a poorly characterized interstitial phosphate-rich phase) and chromite, and only traces of metal and troilite. The individual silicate minerals have normal chondritic REE patterns, but whitlockite has a remarkable REE pattern. It is very enriched in light REE (La is 720X C1, and Lu is 90X C1, as opposed to usual chonditic values of ～300X and 100–150X, respectively) with a negative Eu anomaly. The enrichment of whole rock K is expressed both in an unusually high mean modal Or content of the feldspar, Or₁₃, and in the presence of antiperthite. Whole rock trace element data for the silicate mass support the petrography. Watson silicate was an H-chondrite engulfed by metal and melted at > 1550 °C. A flat refractory lithophile and flat REE pattern (at ～1x average H-chondrites) indicate that melting took place in a relatively closed system. Immiscible metal and sulfide were occluded into the surrounding metal host. Below 1100 °C, the average cooling rate is estimated to have been ～1000 °C/Ma; Widmanstätten structure formed, any igneous zoning in the silicates was equilibrated, and feldspar and pyroxene exsolution took place. Cooling to below 300 °C was completed by 3.5 Ga B. P. At 8 Ma, a shock event took place causing some severe metal deformation and forming local melt pockets of schreibersite/metal. This event likely caused the release of Watson into interplanetary space. The time of this event, 8Ma, corresponds to the peak frequency of exposure ages of the H-chondrites. This further confirms the link between HE irons and the H-chondrites, a relationship already indicated by their common oxygen isotope source. Watson metal structures are very similar to those in Kodaikanal. Watson, Kodaikanal and Netschaëvo form the young group of HE meteorites (ages 3.7 ± 0.2 Ga). They appear to represent steps in a chain of events that must have taken place repeatedly on the HE parent body or bodies from which they came: chondrite engulfed in metal (Netschaëvo); chondrite melted within metal (Watson); and finally melted silicate undergoing strong fractionation with the fractionated material emplaced as globules within metal (Kodaikanal). Watson fills an important gap in understanding the sequence of events that took place in the evolution of the IIE-H parent body(ies). This association of H-chondrite with HE metal suggests a surface, or near surface process-a suggestion made by several other researchers.     

The origin of non-porphyritic pyroxene chondrules in UOCs: Liquid solar nebula condensates?

A total of 56 non-porphyritic pyroxene and pyroxene/olivine micro-objects from different unequilibrated ordinary chondrites were selected for detailed studies to test the existing formation models. Our studies imply that the non-porphyritic objects represent quickly quenched liquids with each object reflecting a very complex and unique evolutionary history. Bulk major element analyses, obtained with EMPA and ASEM, as well as bulk lithophile trace element analyses, determined by LA-ICP-MS, resulted in unfractionated (solar-like) ratios of CaO/Al₂O₃, Yb/Ce as well as Sc/Yb in many of the studied objects and mostly unfractionated refractory lithophile trace element (RLTE) abundance patterns. These features support an origin by direct condensation from a gas of solar nebula composition. Full equilibrium condensation calculations show that it is theoretically possible that pyroxene-dominated non-porphyritic chondrules with flat REE patterns could have been formed as droplet liquid condensates directly from a nebular gas strongly depleted in olivine. Thus, it is possible to have enstatite as the stable liquidus phase in a 800 × Cl dust-enriched nebular gas at a ptot of 10⁻³ atm, if about 72% of the original Mg is removed (as forsterite?) from the system. Condensation of liquids from vapor (primary liquid condensation) could be considered as a possible formation process of the pyroxene-dominated non-porphyritic objects. This process can produce a large spectrum of chemical compositions, which always have unfractionated RLTE abundances. Late stage and subsolidus metasomatic events appear to have furthered the compositional diversity of chondrules and related objects by addition of moderately volatile and volatile elements to these objects by exchange reactions with the chondritic reservoir (e.g., V, Cr, Mn, FeO as well as K and Na). The strong fractionation displayed by the volatile lithophile elements could be indicative of a variable efficiency of metasomatic processes occurring during and/or after chondrule formation. Histories of individual objects differ in detail from each other and clearly indicate individual formation and subsequent processing.     

The composition and thickness of the crust of Mars estimated from rare earth elements and neodymium-isotopic compositions of Martian meteorites

Abstract— Isotopic and trace element compositions of Martian meteorites show that early differentiation of Mars produced complementary crustal and mantle reservoirs that were sampled by later magmatic events. This paper describes a mass balance model that estimates the rare earth element (REE) content and thickness of the crust of Mars from the compositions of shergottites. The diverse REE and Nd isotopic compositions of shergottites are most easily explained by variable addition of light rare earth element (LREE)–enriched crust to basaltic magmas derived from LREE-depleted mantle source regions. Antarctic shergottites EET 79001, ALH 77005, LEW 88516, and QUE 94201 all have strongly LREE-depleted patterns and positive initial ¹⁴³Nd isotopic compositions, which is consistent with the generation of these magmas from depleted mantle sources and little or no interaction with enriched crust. In contrast, Shergotty and Zagami have negative initial ¹⁴³Nd isotopic compositions and less pronounced depletions of the LREE, which have been explained by incorporation of enriched crustal components into mantle-derived magmas (Jones, 1989; Longhi, 1991; Borg et al., 1997). The mass balance model presented here derives the REE composition of the crustal component in Shergotty by assuming it represents a mixture between a mantle-derived magma similar in composition to EET 79001A and a LREE-enriched crustal component. The amount of crust in Shergotty is constrained by mixing relations based on Nd-isotopic compositions, which allows the REE pattern of the crustal component to be calculated by mass balance. The effectiveness of this model is demonstrated by the successful recovery of important characteristics of the Earth's continental crust from terrestrial Columbia River basalts. Self-consistent results for Nd-isotopic compositions and REE abundances are obtained if Shergotty contains ～10–30% of LREE-enriched crust with >10 ppm Nd. This crustal component would have moderately enriched LREE (Sm/Nd = 0.25–0.27; ¹⁴⁷Sm/¹⁴⁴Nd = 0.15–0.17; La/Yb = 2.7–3.8), relatively unfractionated heavy rare earth elements (HREE), and no Eu anomaly. Crust with these characteristics can be produced from a primitive lherzolitic Martian mantle by modest amounts (2–8%) of partial melting, and it would have a globally averaged thickness of <45 km, which is consistent with geophysical estimates. Mars may serve as a laboratory to investigate planetary differentiation by extraction of a primary basaltic crust.     

Magnesian anorthositic granulites in lunar meteorites Allan Hills A81005 and Dhofar 309: Geochemistry and global significance

Abstract– Fragments of magnesian anorthositic granulite are found in the lunar highlands meteorites Allan Hills (ALH) A81005 and Dhofar (Dho) 309. Five analyzed clasts of meteoritic magnesian anorthositic granulite have Mg′ [molar Mg/(Mg + Fe)] = 81–87; FeO ≈ 5% wt; Al₂O₃ ≈ 22% wt; rare earth elements abundances ≈ 0.5–2 × CI (except Eu ≈ 10 × CI); and low Ni and Co in a non‐chondritic ratio. The clasts have nearly identical chemical compositions, even though their host meteorites formed at different places on the Moon. These magnesian anorthositic granulites are distinct from other highlands materials in their unique combination of mineral proportions, Mg′, REE abundances and patterns, Ti/Sm ratio, and Sc/Sm ratio. Their Mg′ is too high for a close relationship to ferroan anorthosites, or to have formed as flotation cumulates from the lunar magma ocean. Compositions of these magnesian anorthositic granulites cannot be modeled as mixtures of, or fractionates from, known lunar rocks. However, compositions of lunar highlands meteorites can be represented as mixtures of magnesian anorthositic granulite, ferroan anorthosite, mare basalt, and KREEP. Meteoritic magnesian anorthositic granulite is a good candidate for the magnesian highlands component inferred from Apollo highland impactites: magnesian, feldspathic, and REE‐poor. Bulk compositions of meteorite magnesian anorthositic granulites are comparable to those inferred for parts of the lunar farside (the Feldspathic Highlands Terrane): ～4.5 wt% FeO; ～28 wt% Al₂O₃; and Th <1 ppm. Thus, magnesian anorthositic granulite may be a widespread and abundant component of the lunar highlands.     

Refractory forsterite in primitive meteorites: Condensates from the solar nebula?

Abstract— All groups of chondritic meteorites contain discrete grains of forsteritic olivine with FeO contents below 1 wt% and high concentrations of refractory elements such as Ca, Al, and Ti. Ten such grains (52 to 754 μg) with minor amounts of adhering matrix were separated from the Allende meteorite. After bulk chemical analysis by instrumental neutron activation analysis (INAA), some samples were analyzed with an electron microprobe and some with an ion microprobe. Matrix that accreted to the forsterite grains has a well‐defined unique composition, different from average Allende matrix in having higher Cr and lower Ni and Co contents, which implies limited mixing of Allende matrix. All samples have approximately chondritic relative abundances of refractory elements Ca, Al, Sc, and rare‐earth elements (REE), although some of these elements, such as Al, do not quantitatively reside in forsterite; whereas others (e.g., Ca) are intrinsic to forsterite. The chondritic refractory element ratios in bulk samples, the generally high abundance level of refractory elements, and the presence of Ca‐Al‐Ti‐rich glass inclusions suggest a genetic relationship of refractory condensates with forsteritic olivine. The Ca‐Al‐Ti‐rich glasses may have acted as nuclei for forsterite condensation. Arguments are presented that exclude an origin of refractory forsterite by crystallization from melts with compositions characteristic of Allende chondrules: (a) All forsterite grains have CaO contents between 0.5 and 0.7 wt% with no apparent zoning, requiring voluminous parental melts with 18 to 20 wt% CaO, far above the average CaO content of Allende chondrules. Similar arguments apply to Al contents. (b) The low FeO content of refractory forsterite of 0.2‐0.4 wt% imposes an upper limit of ～1 wt% of FeO on the parental melt, too low for ordinary and carbonaceous chondrule melts, (c) The Mn contents of refractory forsterites are between 30 to 40 ppm. This is at least one order of magnitude below the Mn content of chondrule olivines in all classes of meteorites. The observed Mn contents of refractory forsterite are much too low for equilibrium between olivine and melts of chondrule composition, (d) As shown earlier, refractory forsterites have O‐isotopic compositions different from chondrules (Weinbruch et al., 1993a). Refractory olivines in carbonaceous chondrites are found in matrix and in chondrules. The compositional similarity of both types was taken to indicate that all refractory forsterites formed inside chondrules (e.g., Jones, 1992). As refractory forsterite cannot have formed by crystallization from chondrule melts, we conclude that refractory forsterite from chondrules are relic grains that survived chondrule melting and probably formed in the same way as refractory forsterite enclosed in matrix. We favor an origin of refractory forsterite by condensation from an oxidized nebular gas.     

The White Angel: A unique wollastonite‐bearing,mass‐fractionated refractory inclusion from the Leoville CV3 carbonaceous chondrite

Abstract— We report the study of an unusual compact type A refractory inclusion, named the White Angel, from the Leoville CV3 meteorite. The petrologic, mineral chemical, isotopic, and trace‐element signatures of this once‐molten Ca‐Al‐rich inclusion (CAI), which contains large, equant wollastonite crystals, indicate a short multistage history that occurred very early, before substantial decay of ²⁶Al. Magnesium in the inclusion is isotopically heavy, with F_Mg reaching 18‰/amu, in the range of fractionated and with unidentified nuclear effects (FUN) inclusions. However, the absence of any nuclear anomalies in Ca and Ti and an inferred ²⁶Al/²⁷Al ratio of (5.5 ± 0.9) × 10^?5 indicate that the White Angel belongs to the F inclusions. Silicon and oxygen are also mass fractionated in favor of the heavy isotopes, but to a lesser extent. The O isotopes show a range in ¹⁶O excesses. On an O three‐isotope plot, data points lie on a line parallel and to the right of the carbonaceous chondrite anhydrous mineral mixing line, with wollastonite being the most ¹⁶O‐rich phase. The chondrite‐normalized rare earth and trace‐element pattern of the whole inclusion is the complement of an ultrarefractory pattern indicating that precursor phases of the CAI must have condensed in an Al‐, heavy rare earth element (HREE)‐depleted reservoir. Melting of those precursor phases in an ¹⁶O‐rich environment and evaporation led to mass‐dependent isotopic fractionation of Mg, Si, and O. Partial isotopic exchange with a reservoir containing unfractionated Mg took place at a later stage but before any measurable decay of ²⁶Al. Some minerals (melilite and perovskite) in the White Angel equilibrated oxygen isotopes with a relatively ¹⁶O‐poor reservoir that was also mass‐fractionated toward the heavy isotopes, different from that with which the normal or FUN inclusions interacted.     

Detailed abundances of rare earth elements,thorium and uranium in chondritic meteorites: An ICP-MS study

Abstract— Inductively coupled plasma mass spectrometry (ICP-MS) was successfully applied to bulk samples of Allende, Jilin, Modoc, Saint-Séverin and Atlanta for the determination of rare earth elements (REE) (Y and 14 lanthanoids), Th and U. The results of ICP-MS showed good agreement with recommended values, and their reproducibilities were high enough to discuss the detailed abundances of lanthanoids and actinoids in chondritic meteorites. For the Allende reference sample issued by the Smithsonian Institution, a positive anomaly of Tm, a fractionation between light REE and heavy REE and a high Th/U ratio were observed in the CI-normalized abundances of REE, Th and U. These features are common for group II inclusions in Allende, suggesting that the abundances of refractory lithophiles in Allende are somewhat influenced by those in a specific constituent. For the other chondritic meteorites, a zigzag alteration was commonly observed in the heavy-REE region of their CI-normalized abundance patterns. It is suggested that such a zigzag pattern is attributable to erratically high abundances of monoisotopic REE (Tb, Ho and Tm) in the CI values. Abundances of REE, Th and U in the bulk samples are also discussed separately in detail.     

A hibonite‐corundum inclusion from Murchison: A first‐generation condensate from the solar nebula

Abstract— Through freeze‐thaw disaggregation of the Murchison (CM) carbonaceous chondrite, we have recovered a ?90 times 75 μm refractory inclusion that consists of corundum and hibonite with minor perovskite. Corundum occurs as small (?10 μm), rounded grains enclosed in hibonite laths (?10 μm wide and 30–40 μm long) throughout the inclusion. Perovskite predominantly occurs near the edge of the inclusion. The crystallization sequence inferred petrographically‐corundum followed by hibonite followed by perovskite‐is that predicted for the first phases to form by equilibrium condensation from a solar gas for P^tot ≤5 times 10^?3 atm. In addition, the texture of the inclusion, with angular voids between subhedral hibonite laths and plates, is also consistent with formation of the inclusion by condensation. Hibonite has heavy rare earth element (REE) abundances of ?40 × CI chondrites, light REE abundances ?20 × CI chondrites, and negative Eu anomalies. The chondrite‐normalized abundance patterns, especially one for a hibonite‐perovskite spot, are quite similar to the patterns of calculated solid/gas partition coefficients for hibonite and perovskite at 10^?3 atm and are not consistent with formation of the inclusion by closed‐system fractional crystallization. In contrast with the features that are consistent with a condensation origin, there are problems with any model for the formation of this inclusion that includes a molten stage, relic grains, or volatilization. If thermodynamic models of equilibrium condensation are correct, then this inclusion formed at pressures <5 times 10^?3 atm, possibly with enrichments (<1000x) in CI dust relative to gas at low pressures (below 10^?4 atm). Both hibonite and corundum have δ17O ? δ18O ? ?50%, indicating formation from an 16O‐rich source. The inclusion does not contain radiogenic ²⁶Mg and apparently did not contain live ²⁶Al when it formed. If the short‐lived radionuclides were formed in a supernova and injected into the early solar nebula, models of this process suggest that ²⁶Al‐free refractory inclusions such as this one formed within the first ?6 times 10⁵ years of nebular collapse.