On the significance of diopside and oldhamite in enstatite chondrites and aubrites

Abstract— Enstatite is the primary silicate phase of equilibrated enstatite chondrites (EECs). The CaO contents of these enstatites lie close to or on the enstatite-diopside phase boundary, yet, curiously, diopside has always been absent from EEC assemblages. In contrast, aubrites contain abundant diopside even though they are thought to be derived from an E chondrite-like protolith. A phase equilibrium analysis of the Ca-Mg-Fe-Mn-Si-O-S system under reducing conditions solves this enigma and shows that diopside-bearing EECs should commonly be found. When S fugacity is sufficiently high (e.g., Fe-FeS buffer), low O fugacity limits the stability of diopside in favor of oldhamite. Under such conditions, the relative stability of diopside and oldhamite is described by the reaction: CaMgSi₂O₆ + MgS = CaS + Mg₂Si₂O₆ A large bulk compositional field exists where diopside and oldhamite are simultaneously stable. The existence of oldhamite does not preclude the stability of diopside. Phase diagram topology demonstrates that bulk compositions lying in the enstatite-oldhamite field and enstatite-oldhamite-alabandite field have enstatite CaO contents nearly identical to that of enstatite in equilibrium with diopside alone. This explains the high enstatite CaO contents of all EECs that do not contain diopside. This study also reports the discovery of the first EEC to contain metamorphic diopside, the Antarctic meteorite EET 90102. Elephant Moraine 90102 has a typical EL6 texture and contains the assemblage: enstatite, diopside, albite, kamacite, troilite, sinoite, and graphite. Trace quantities of alabandite, oldhamite and daubreelite are also present. Diopside is stable in EET 90102 because its bulk composition lies within either the enstatite-diopside-oldhamite-alabandite or diopside-alabandite-enstatite stability fields. In contrast, all other EECs analyzed to date have bulk compositions lying in the enstatite-oldhamite-alabandite stability field. The discovery of diopside in EET 90102 helps confirm the predictions of the phase equilibrium analysis. Elephant Moraine 90102 experienced a high-temperature metamorphic equilibration from which it was quenched. The enstatite-diopside, CaS in alabandite and Fe in alabandite, geothermometers yield temperatures of last equilibration of ～900 °C. The absence of daubreelite and schreibersite along with high troilite Cr contents and high kamacite P contents confirm a high-temperature metamorphic quench. The EET 90102 chondrite experienced a somewhat different cooling history and has a slightly different bulk composition than all other EECs studied to date; however, the close mineralogic, petrologic and textural similarities between EET 90102 and nominal EL6 chondrites signify that it should be classified as a diopside- and sinoite-bearing EL6 chondrite. Assuming that the aubrites formed from an E chondrite-like protolith, a source rock similar to that of a diopside-bearing EEC offers a clear advantage for aubrite formation. Melting of a diopside-saturated EEC protolith would not require conversion of CaS to achieve diopside-saturation upon cooling.     

Trace elements in mineral separates of the Peña Blanca Spring aubrite: Implications for the evolution of the aubrite parent body

Abstract— The origin of the aubrite parent body (APB) and its relation to the enstatite chondrites is still unclear. Therefore we began a detailed chemical study of the aubrite Peña Blanca Spring. Bulk samples and mineral separates (oldhamite, troilite, alabandite, pyroxene) of Peña Blanca Spring were analyzed for major and trace elements by instrumental neutron activation analysis (INAA). In addition, a leaching experiment was performed on a powdered bulk sample to study the distribution of trace elements in aubrite minerals. The elemental abundances in Peña Blanca Spring are compared to abundances in EH-chondrites and EL-chondrites in an attempt to distinguish volatility related fractionations (evaporation, condensation) from planetary differentiation (melting and core formation). Low abundances of siderophile (e.g., Ir) and chalcophile (e.g., V) elements in bulk samples indicate that 25% (by mass) metal and about 6% (by mass) sulfide separated from an enstatite chondrite like-parent body to form a core and a residual mantle with aubrite composition. We argue that the high observed rare earth element (REE) abundances in oldhamite (>100 × EH-chondrite normalized) reflect REE incorporation into oldhamite during nebular condensation. Thus, oldhamite in aubrites is, at least in part, a relict phase as originally proposed by Lodders and Palme (1990). Some re-equilibration of CaS with silicates has, however, occurred, leading to partial redistribution of REE, as exemplified by the uptake of Eu by plagioclase. The distribution of the REE among aubritic minerals cannot be the result of fractional crystallization, which would occur if high degrees of partial melting took place on the APB. Instead, the REE distributions indicate incomplete equilibrium of oldhamite and other phases. Therefore, a short non-equlibrium melting episode led to segregation of metal and sulfides.     

The evolution of enstatite and chondrules in unequilibrated enstatite chondrites: Evidence from iron-rich pyroxene

Abstract— FeO-rich (Fs^6–34) pyroxene lacking cathodoluminescence (CL), hereafter black pyroxene, is a major constituent of some of the chondrules and fragments in unequilibrated (type 3) enstatite chondrites (UECs). It contains structurally oriented zones of Cr-, Mn-, V-rich, FeO-poor enstatite with red CL, associated with mm-sized blebs of low-Ni, Fe-metal and, in some cases, silica. These occurrences represent clear evidence of pyroxene reduction. The black pyroxene is nearly always rimmed by minor element (Cr, Mn, V)-poor enstatite having a blue CL. More commonly, red and blue enstatites, unassociated with black pyroxene, occur as larger grains in chondrules and fragments, and these constitute the major silicate phases in UECs. The REE abundance patterns of the black pyroxene are LREE-depleted. The blue enstatite rims, however, have a near-flat to LREE-enriched pattern, ～0.5–4x chondritic. The petrologic and trace element data indicate that the black pyroxene is from an earlier generation of chondrules that formed in a nebular region that was more oxidizing than that of the enstatite chondrites. Following solidification, these chondrules experienced a more reducing nebular environment and underwent reduction. Some, perhaps most, of the red enstatite that is common throughout the UECs may be the product of solid-state reduction of black pyroxene. The blue enstatite rims grew onto the surfaces of the black pyroxene and red enstatite as a result of condensation from a nebular gas. The evolutionary history of some of the enstatite and chondrules in enstatite chondrites can be expressed in a four-stage model that includes: Stage 1. Formation of chondrules in an oxidizing nebular environment Stage 2. Solid-state reduction of the more oxidized chondrules and fragments to red enstatite in a more reducing nebular environment Stage 3. Formation of blue enstatite rims on the black pyroxene as well as on the red enstatite. Stage 4. Reprocessing, by various degrees of melting, of many of the earlier-formed materials.     

The formation conditions of enstatite chondrites: Insights from trace element geochemistry of olivine‐bearing chondrules in Sahara 97096 (EH3)

We report in situ LA‐ICP‐MS trace element analyses of silicate phases in olivine‐bearing chondrules in the Sahara 97096 (EH3) enstatite chondrite. Most olivine and enstatite present rare earth element (REE) patterns comparable to their counterparts in type I chondrules in ordinary chondrites. They thus likely share a similar igneous origin, likely under similar redox conditions. The mesostasis however frequently shows negative Eu and/or Yb (and more rarely Sm) anomalies, evidently out of equilibrium with olivine and enstatite. We suggest that this reflects crystallization of oldhamite during a sulfidation event, already inferred by others, during which the mesostasis was molten, where the complementary positive Eu and Yb anomalies exhibited by oldhamite would have possibly arisen due to a divalent state of these elements. Much of this igneous oldhamite would have been expelled from the chondrules, presumably by inertial acceleration or surface tension effects, and would have contributed to the high abundance of opaque nodules found outside them in EH chondrites. In two chondrules, olivine and enstatite exhibit negatively sloped REE patterns, which may be an extreme manifestation of a general phenomenon (possibly linked to near‐liquidus partitioning) underlying the overabundance of light REE observed in most chondrule silicates relative to equilibrium predictions. The silicate phases in one of these two chondrules show complementary Eu, Yb, and Sm anomalies providing direct evidence for the postulated occurrence of the divalent state for these elements at some stage in the formation reservoir of enstatite chondrites. Our work supports the idea that the peculiarities of enstatite chondrites may not require a condensation sequence at high C/O ratios as has long been believed.     

Partial melting of the Indarch (EH4) meteorite: A textural,chemical, and phase relations view of melting and melt migration

Abstract— To test whether aubrites can be formed by melting of enstatite chondrites and to understand igneous processes at very low O fugacities, we have conducted partial melting experiments on the Indarch (EH4) chondrite at 1000–1500 °C. Silicate melting begins at 1000 °C, and Indarch is completely melted by 1500 °C. The metal-sulfide component melts completely at 1000 °C. Substantial melt migration occurs at 1300–1400 °C, and metal migrates out of the silicate charge at 1450 °C and ～50% silicate partial melting. As a group, our experiments contain three immiscible metallic melts (Si-, P-, and C-rich), two immiscible sulfide melts (Fe- and FeMgMnCa-rich), and silicate melt. Our partial melting experiments on the Indarch (EH4) enstatite chondrite suggest that igneous processes at low fO₂ exhibit several unique features. The complete melting of sulfides at 1000 °C suggests that aubritic sulfides are not relics. Aubritic oldhamite may have crystallized from Ca and S complexed in the silicate melt. Significant metal-sulfide melt migration might occur at relatively low degrees of silicate partial melting. Substantial elemental exchange occurred between different melts (e.g., S between sulfide and silicate, Si between silicate and metal), a feature not observed during experiments at higher fO₂. This exchange may help explain the formation of aubrites from known enstatite chondrites.     

Reclassification of four aubrites as enstatite chondrite impact melts: Potential geochemical analogs for Mercury

We present petrologic and isotopic data on Northwest Africa (NWA) 4799, NWA 7809, NWA 7214, and NWA 11071 meteorites, which were previously classified as aubrites. These four meteorites contain between 31 and 56 vol% of equigranular, nearly endmember enstatite, Fe,Ni metal, plagioclase, terrestrial alteration products, and sulfides, such as troilite, niningerite, daubréelite, oldhamite, and caswellsilverite. The equigranular texture of the enstatite and the presence of the metal surrounding enstatite indicate that these rocks were not formed through igneous processes like the aubrites, but rather by impact processes. In addition, the presence of pre‐terrestrially weathered metal (7.1–14 vol%), undifferentiated modal abundances compared to enstatite chondrites, presence of graphite, absence of diopside and forsterite, low Ti in troilite, and high Si in Fe,Ni metals suggest that these rocks formed through impact melting on chondritic and not aubritic parent bodies. Formation of these meteorites on a parent body with similar properties to the EHa enstatite chondrite parent body is suggested by their mineralogy. These parent bodies have undergone impact events from at least 4.5 Ga (NWA 11071) until at least 4.2 Ga (NWA 4799) according to ³⁹Ar‐⁴⁰Ar ages, indicating that this region of the solar system was heavily bombarded early in its history. By comparing NWA enstatite chondrite impact melts to Mercury, we infer that they represent imperfect petrological analogs to this planet given their high metal abundances, but they could represent important geochemical analogs for the behavior and geochemical affinities of elements on Mercury. Furthermore, the enstatite chondrite impact melts represent an important petrological analog for understanding high‐temperature processes and impact processes on Mercury, due to their similar mineralogies, Fe‐metal‐rich and FeO‐poor silicate abundances, and low oxygen fugacity.     

Experimental rare-earth-element partitioning in oldhamite: Implications for the igneous origin of aubritic oldhamite

Abstract— Aubritic oldhamite (CaS) has been the subject of intense study recently because it is the major rare-earth-element (REE) carrier in aubrites, has a variety of REE patterns comparable to those in unequilibrated enstatite chondrites and has an extraordinarily high melting point as a pure substance (2525 °C). These latter two facts have caused some authors to assert that much of the aubritic oldhamite is an unmelted nebular relict, rather than of igneous origin. We have conducted REE partitioning experiments between oldhamite and silicate melt using an aubritic bulk composition at 1200 °C and 1300 °C and subsolidus annealing experiments. All experiments produced crystalline oldhamite, with a range of compositions, glass and Fe metal, as well as enstatite, SiO₂, diopside and troilite in some charges. Rare-earth-element partitioning is strongly dependent on oldhamite composition and temperature. Subsolidus annealing results in larger partition coefficients for some oldhamite grains, particularly those in contact with troilite. All experimental oldhamite/silicate melt partition coefficients are <20 and the vast majority are <5, which is similar to those reported in the literature and is two orders of magnitude less than those inferred for natural aubritic oldhamite. These partition coefficients preclude a simple igneous model, since REE abundances in aubritic oldhamite are greater than would be predicted on the basis of the experimental partition coefficients. Our experimental partition coefficients are consistent with a relict nebular origin for aubritic oldhamite, although experimental evidence that suggests melting of oldhamite at temperatures lower than that reached on the aubrite parent body are clearly inconsistent with the nebular model. Our experiments are consistent also with a complex igneous history. Oldhamite REE patterns may reflect a complex process of partial melting, melt removal, fractional crystallization and subsolidus annealing and exsolution. These mechanisms (primarily fractional crystallization and subsolidus annealing) can produce a wide range of REE patterns in aubritic oldhamite, as well as elevated (100–1000 × CI) REE abundances observed in aubritic oldhamite.     

Raman spectroscopy of shocked enstatite-rich meteorites

We present Raman patterns of enstatite in different classes of enstatite-rich chondrites and achondrites of various shock levels as previously reported from petrographic observations and X-ray diffraction analyses. Thin sections or mineral separates of four enstatite chondrites (LaPaz Icefield [LAP] 02225, MacAlpine Hills [MAC] 02837, Pecora Escarpment [PCA] 91020, and Itqiy), three aubrites (Larkman Nunatak [LAR] 04316, Khor Temiki, and Allan Hills [ALH] 84008), and a ureilite (Sayh al Uhaymir [SaU] 559) were examined by laser Raman spectroscopy. We find that the frequencies of fundamental Raman peaks of enstatites from the chondrites and aubrites deviate by ≤2 cm⁻¹ from the values for unshocked enstatite. This small difference implies a negligible effect of shock metamorphism on peak positions. Significant differences (<6 cm⁻¹) for peak positions are found for the pyroxenes of SaU 559 and may be attributed to minor substitution of Fe and Ca for Mg. Linear regressions of peak widths of enstatite chondrites against their established shock stages show a strong positive correlation for each mode (r² > 0.94). From this linear relationship, the 343 and 1014 cm⁻¹ peaks of the aubrites coincide with S4 determined from petrography. For Itqiy, we find S4–5, while the shock levels of SaU 559 exceed the petrologic scheme (S1–6), suggesting that the ureilite might have sustained multiple shock events or have been deformed in a high-pressure environment. Alternatively, for Itqiy (peak 343 cm⁻¹) and SaU 559 (all peaks) enstatites, minor substitutions of Fe and Ca for Mg may have further broadened their peak widths.     

Dark clasts in the Khor Temiki aubrite: Not basalts

Abstract— The enstatite achondrite meteorites (aubrites) are ultramafic assemblages with highly variable bulk rare earth element (REE) compositions. An enrichment of REE in a dark clast from the Khor Temiki aubrite led Wolf et al. (1983) to suggest that such dark clasts could be the basaltic (i.e., enstatite-plagioclase) complements to the ultramafic aubrites, with the relatively high REE contents resulting from the presence of plagioclase, which is a common carrier of the REEs. We have studied several dark clasts from the Khor Temiki aubrite and find no evidence for a basaltic character for such material. The microscopic character of the dark clasts is not significantly different from the main portions of Khor Temiki and consists either of highly brecciated material, containing a fine-grained matrix, or of enstatite grains with abundant inclusions. We suggest that the dark clasts are shock-darkened, heterogeneous Khor Temiki material that, by chance, contained variable trace contents of oldhamite (CaS), which has been shown to be a major carrier of REE in aubrites. We find that the REE contents of the clasts range from 0.1 to ～20× CI. Most have negative Eu anomalies, but one has a small positive anomaly. Extensive searches have failed to identify basaltic material in Khor Temiki and other aubrites. The absence of basaltic material is consistent with, but does not prove, the model of Wilson and Keil (1991). They calculate that, on an asteroidal parent body < ～100 km in radius, a volatile-rich basaltic partial melt erupted with a velocity greater than the escape velocity of the asteroid and, thus, was lost into space ～ 4.55 Ga ago.     

A multi‐step model for the origin of E3 (enstatite) chondrites

Abstract— It appears that the mineralogy and chemical properties of type 3 enstatite chondrites could have been established by fractionation processes (removal of a refractory component, and depletion of water) in the solar nebula, and by equilibration with nebular gas at low‐to‐intermediate temperatures (approximately 700–950 K). We describe a model for the origin of type 3 enstatite chondrites that for the first time can simultaneously account for the mineral abundances, bulk‐chemistry, and phase compositions of these chondrites by the operation of plausible processes in the solar nebula. This model, which assumes a representative nebular gas pressure of 10^?5 bar, entails three steps: (1) initial removal of 56% of the equilibrium condensed phases in a system of solar composition at 1270 K; (2) an average loss of 80–85% water vapor in the remaining gas; and (3) two different closure temperatures for the condensed phases. The first step involves a “refractory element fractionation” and is needed to account for the overall major element composition of enstatite chondrites, assuming an initial system with a solar composition. The second step, water‐vapor depletion, is needed to stabilize Si‐bearing metal, oldhamite, and niningerite, which are characteristic minerals of the enstatite chondrites. Variations in closure temperatures are suggested by the way in which the bulk chemistry and mineral assemblages of predicted condensates change with temperature, and how these parameters correlate with the observations of enstatite chondrites. In general, most phases in type 3 enstatite chondrites appear to have ceased equilibrating with nebular gas at approximately 900–950 K, except for Fe‐metal, which continued to partially react with nebular gas to temperatures as low as ～700 K.     

Enstatite aggregates with niningerite,heideite, and oldhamite from the Kaidun carbonaceous chondrite: Relatives of aubrites and EH chondrites?

Abstract— We studied 2 enstatite aggregates (En >99), with sizes of 0.5 and 1.5 mm, embedded in the carbonaceous matrix of Kaidun. They contain sulfide inclusions up to 650 μm in length, which consist mainly of niningerite but contain numerous grains of heideite as well as oldhamite and some secondary phases (complex Fe, Ti, S hydroxides and Ca carbonate). Both niningerite and heideite are enriched in all trace elements relative to the co‐existing enstatite except for Be and Sc. The niningerite has the highest Ca content (about 5 wt%) of all niningerites analyzed so far in any meteorite and is the phase richest in trace elements. The REE pattern is fractionated, with the CI‐normalized abundance of Lu being higher by 2 orders of magnitude than that of La, and has a strong negative Eu anomaly. Heideite is, on average, poorer in trace elements except for Zr, La, and Li. Its REE pattern is flat at about 0.5 × CI, and it also has a strong negative Eu anomaly. The enstatite is very poor in trace elements. Its Ce content is about 0.01 that of niningerite, but Li, Be, Ti, and Sc have between 0.1 and 1 × CI abundances. The preferential partitioning of typical lithophile elements into sulfides indicates highly O‐deficient and S‐dominated formation conditions for the aggregates. The minimum temperature of niningerite formation is estimated to be ?850–900 °C. The texture and the chemical characteristics of the phases in the aggregates suggest formation by aggregation and subsequent sintering before incorporation into the Kaidun breccia. The trace element data obtained for heideite, the first on record, show that this mineral, in addition to oldhamite and niningerite, is also a significant carrier of trace elements in enstatite meteorites.     

Enstatite meteorites and their parent bodies*

Abstract— Enstatite meteorites are highly reduced rocks that consist of major, nearly FeO-free enstatite, variable amounts of metallic Fe, Ni and troilite, and a host of rare minerals formed under highly-reducing conditions. They are comprised of the EH and EL chondrites and the aubrites. Here I discuss some of their properties and the nature and number of their parent bodies. Conclusions: 1. EH and EL chondrites show bulk compositional differences in non-volatile major elements that were established by nebular, not planetary processes. Occurrence of abundant breccias among them but lack of clasts of EL in EH chondrites (and vice versa) suggests that EH and EL chondrites represent two separate parent bodies. 2. Aubrites were not derived from known enstatite chondrites on the same parent bodies. Aubrites represent samples from a third enstatite meteorite parent body. 3. The aubrite parent body may have experienced collisional break-up and gravitational reassembly of the debris into a rubble-pile object. 4. The aubrite source material (parent body) was probably enstatite chondrite-like in composition, but had a higher troilite/metallic Fe, Ni ratio, higher contents of titanium and diopside, and possibly less plagioclase than known enstatite chondrites. 5. Shallowater, the only non-brecciated aubrite, does not appear to have formed on the EH, EL, or aubrite parent bodies by either internal (igneous) or external (impact) melting processes. Instead, Shallowater may be a sample from yet a fourth enstatite meteorite parent body. 6. Shallowater experienced a complex three-stage cooling history, requiring an equally complex mode of origin: collisional break-up of a molten or partly molten body by impact with a solid body, followed by gravitational reassembly. 7. It is unknown why some enstatite meteorite parent bodies melted (the aubrite and Shallowater bodies), and others did not (the EH and EL bodies). If unipolar dynamo induction by a primordial T Tauri sun was the dominant heat source that heated asteroidal-sized bodies in the early Solar System, then the aubrite and Shallowater parent bodies may have melted because they were of intermediate sizes, whereas the EH and EL bodies did not melt because they were either much smaller or much larger.     

Calcium‐aluminum‐rich inclusions in enstatite chondrites (I): Mineralogy and textures

Abstract— Like calcium‐aluminum‐rich inclusions (CAIs) from carbonaceous and ordinary chondrites, enstatite chondrite CAIs are composed of refractory minerals such as spinel, perovskite, Al, Ti‐diopside, melilite, hibonite, and anorthitic plagioclase, which may be partially to completely surrounded by halos of Na‐(±Cl)‐rich minerals. Porous, aggregate, and compact textures of the refractory cores in enstatite chondrite CAIs and rare Wark—Lovering rims are also similar to CAIs from other chondrite groups. However, the small size (<100μm), low abundance (<1% by mode in thin section), occurrence of only spinel or hibonite‐rich types, and presence of primary Ti‐(±V)‐oxides, and secondary geikelite and Ti, Fe‐sulfides distinguish the assemblage of enstatite chondrite CAIs from other groups. The primary mineral assemblage in enstatite chondrite CAIs is devoid of indicators (e.g., oldhamite, osbornite) of low O fugacities. Thus, high‐temperature processing of the CAIs did not occur under the reducing conditions characteristic of enstatite chondrites, implying that either (1) the CAIs are foreign to enstatite‐chondrite‐forming regions or (2) O fugacities fluctuated within the enstatite‐chondrite‐forming region. In contrast, secondary geikelite and Ti‐Fe‐sulfide, which replace perovskite, indicate that alteration of perovskite occurred under reducing conditions distinct from CAIs in the other chondrite groups. We have not ascertained whether the reduced alteration of enstatite chondrite CAIs occurred in a nebular or parent‐body setting. We conclude that each chondrite group is correlated with a unique assemblage of CAIs, indicating spatial or temporal variations in physical conditions during production or dispersal of CAIs.     

Nonporphyritic chondrules and chondrule fragments in enstatite chondrites: Insights into their origin and secondary processing

Sixteen nonporphyritic chondrules and chondrule fragments were studied in polished thin and thick sections in two enstatite chondrites (ECs): twelve objects from unequilibrated EH3 Sahara 97158 and four objects from equilibrated EH4 Indarch. Bulk major element analyses, obtained with electron microprobe analysis (EMPA) and analytical scanning electron microscopy (ASEM), as well as bulk lithophile trace element analyses, determined by laser ablation inductively coupled plasma–mass spectrometry (LA‐ICP‐MS), show that volatile components (K₂O + Na₂O versus Al₂O₃) scatter roughly around the CI line, indicating equilibration with the chondritic reservoir. All lithophile trace element abundances in the chondrules from Sahara 97158 and Indarch are within the range of previous analyses of nonporphyritic chondrules in unequilibrated ordinary chondrites (UOCs). The unfractionated (solar‐like) Yb/Ce ratio of the studied objects and the mostly unfractionated refractory lithophile trace element (RLTE) abundance patterns indicate an origin by direct condensation. However, the objects possess subchondritic CaO/Al₂O₃ ratios; superchondritic (Sahara 97158) and subchondritic (Indarch) Yb/Sc ratios; and chondritic‐normalized deficits in Nb, Ti, V, and Mn relative to RLTEs. This suggests a unique nebular process for the origin of these ECs, involving elemental fractionation of the solar gas by the removal of oldhamite, niningerite, and/or another phase prior to chondrule condensation. A layered chondrule in Sahara 97158 is strongly depleted in Nb in the core compared to the rim, suggesting that the solar gas was heterogeneous on the time scales of chondrule formation. Late stage metasomatic events produced the compositional diversity of the studied objects by addition of moderately volatile and volatile elements. In the equilibrated Indarch chondrules, this late process has been further disturbed, possibly by a postaccretional process (diffusion?) that preferentially mobilized Rb with respect to Cs in the studied objects.     

Infrared transmission spectra from 2.5 to 25 μm of various meteorite classes

Infrared transmission spectra from 53 meteorites in the spectral range from 2.5 to 25 μm were measured to permit comparisons with data of astronomical objects that are potential meteorite sources. Data were taken for 14 carbonaceous chondrites, 5 LL ordinary chondrites, 6 L ordinary chondrites, 10 H ordinary chondrites, 1 enstatite chondrite, 4 aubrites, 3 eucrites, 4 howardites, 1 diogenite, 1 mesosiderite, 2 nakhlites, 1 shergottite, and the anomalous achondrite Angra dos Reis. The CO and CV carbonaceous chondrites have spectra similar to each other, with 10-μm features characteristic of olivine. The CM carbonaceous chondrites have distinctive 10-μm features that are attributed to layer lattice silicates. Members of both the CI and CR classes have spectra distinct from those of other carbonaceous chondrites. The LL, L, and H ordinary chondrites have spectra that match those of olivine and pyroxene mixtures. The enstatite chondrites and enstatite achondrites (aubrites) all exhibit spectra diagnostic of the pyroxene enstatite. The angrite, howardites, aucrites, nakhlites, shergottite, and diogenite all have similar spectra also dominated by pyroxene. The single mesosiderite examined had a spectrum distinct from all the other meteorites.     

Potassium isotopic compositions of enstatite meteorites

Enstatite chondrites and aubrites are meteorites that show the closest similarities to the Earth in many isotope systems that undergo mass‐independent and mass‐dependent isotopic fractionations. Due to the analytical challenges to obtain high‐precision K isotopic compositions in the past, potential differences in K isotopic compositions between enstatite meteorites and the Earth remained uncertain. We report the first high‐precision K isotopic compositions of eight enstatite chondrites and four aubrites and find that there is a significant variation of K isotopic compositions among enstatite meteorites (from ?2.34‰ to ?0.18‰). However, K isotopic compositions of nearly all enstatite meteorites scatter around the bulk silicate earth (BSE) value. The average K isotopic composition of the eight enstatite chondrites (?0.47 ± 0.57‰) is indistinguishable from the BSE value (?0.48 ± 0.03‰), thus further corroborating the isotopic similarity between Earth's building blocks and enstatite meteorite precursors. We found no correlation of K isotopic compositions with the chemical groups, petrological types, shock degrees, and terrestrial weathering conditions; however, the variation of K isotopes among enstatite meteorite can be attributed to the parent‐body processing. Our sample of the main‐group aubrite MIL 13004 is exceptional and has an extremely light K isotopic composition (δ⁴¹K = ?2.34 ± 0.12‰). We attribute this unique K isotopic feature to the presence of abundant djerfisherite inclusions in our sample because this K‐bearing sulfide mineral is predicted to be enriched in ³⁹K during equilibrium exchange with silicates.     

The oxygen‐isotopic record in enstatite meteorites

Abstract— Oxygen‐isotopic compositions were determined for a suite of enstatite chondrites and aubrites. In agreement with previous work (Clayton et al., 1984), most samples have O‐isotopic compositions close to the terrestrial fractionation line (TFL), and there appear to be no significant differences in O‐isotopic compositions between individual EH and EL chondrites and aubrites. Five enstatite meteorites have O‐isotopic compositions that are significantly different from the other samples and >0.2% away from the TFL. Two of these have petrographic evidence of brecciation and interaction between other meteorite types; for the other three, similar scenarios are suggested. There appears to be a systematic increase in δ¹⁸O from enstatite chondrites (both EH and EL) of petrologic type 3 to those of type 6. There is also good evidence that the EH meteorites do not fall along a mass fractionation line but along a line slope 0.66. At the present time, detailed understanding of the origin of these O‐isotopic systematics remain elusive but clearly point to a complex accretion history, parent‐body evolution, or both.     

An experimental and theoretical study of rare-earth-element partitioning between sulfides (FeS,CaS) and silicate and applications to enstatite achondrites

Abstract— Partition coefficients of the rare-earth-elements (REE) between sulfides (FeS or CaS) and silicate melt were determined experimentally at 1200–1300 °C. The REE sulfide/silicate partition coefficients (D) are ≤1 under the experimental O and S fugacities, which demonstrates that the REE are mainly located in the silicate phase. Rare-earth-element partition coefficients in the FeS/silicate system decrease from light to heavy REE, while the opposite behavior is found for the CaS/silicate system, where partition coefficients increase from light to heavy REE. In both sulfide systems, Eu is preferentially incorporated into the sulfide phases, as also expected from thermodynamic calculations. The Eu sulfide/silicate partition coefficient is about a factor of ten higher than that of neighboring Sm and Gd, in accordance with thermodynamic predictions of REE sulfide/silicate partition coefficients. The low sulfide/silicate partition coefficients indicate that CaS (oldhamite) in enstatite achondrites (aubrites) cannot have gained its high REE concentrations during igneous differentiation processes. The high REE concentrations and the REE patterns in aubritic oldhamite are more plausibly explained by REE condensation into refractory CaS. The refractory nature of CaS prevented major exchange reactions of the oldhamite with other aubritic minerals during the short differentiation and metamorphism period on the aubrite parent body. Thus, oldhamite in aubrites may be relict condensates altered to different degrees during short heating events, as originally suggested by Lodders and Palme (1990).     

The thermometry of enstatite chondrites: A brief review and update

Abstract— Due to the discoveries in Antarctica, the number of known enstatite chondrites has doubled in the last few years, and many rare or previously unknown types have been collected, most notably many EL3 and EH3 chondrites. We have applied the five major enstatite chondrite thermometers to the new and previously known enstatite chondrites, the thermometers being: (1) kamacite-quartz-enstatite-oldhamite-troilite (KQEOT), (2) oldhamite, (3) alabandite-niningerite, (4) sphalerite, and (5) phosphide-metal. Measured temperatures based on the KQEOT and oldhamite systems are 800 °C-1000 °C with the type 3 enstatite chondrites having values similar to those of type 4–6. It seems likely that these temperatures relate to events prior to parent body metamorphism, such as nebula condensation or chondrule formation, and were not significantly reset by later events. Measured temperatures for alabandite-niningerite, metal-phosphide and sphalerite in EH chondrites increase from 300 °C-400 °C to 600 °C-800 °C with petrographic indications of increasing metamorphism. In contrast, measured temperatures for all EL chondrites, including the most heavily metamorphosed, are generally <400 °C. Apparently EL chondrites cooled more slowly than the EH chondrites regardless of metamorphism experienced. Measured temperatures for the alabandite-niningerite, metal-phosphide and sphalerite are actually closure temperatures for the last thermal event suffered by the meteorite, and the fast cooling rates indicated are most consistent with processes occurring in thick regoliths.     

Raman spectroscopic properties and Raman identification of CaS‐MgS‐MnS‐FeS‐Cr2FeS4 sulfides in meteorites and reduced sulfur‐rich systems

Raman spectra were acquired on a series of natural and synthetic sulfide minerals, commonly found in enstatite meteorites: oldhamite (CaS), niningerite or keilite ((Mg,Fe)S), alabandite (MnS), troilite (FeS), and daubreelite (Cr₂FeS₄). Natural samples come from three enstatite chondrites, three aubrites, and one anomalous ungrouped enstatite meteorite. Synthetic samples range from pure endmembers (CaS, FeS, MgS) to complex solid solutions (Fe, Mg, Ca)S. The main Raman peaks are localized at 225, 285, 360, and 470 cm^?1 for the Mg‐rich sulfides; at 185, 205, and 285 cm^?1 for the Ca‐rich sulfides; at 250, 370, and 580 cm^?1 for the Mn‐rich sulfides; at 255, 290, and 365 cm^?1 for the Cr‐rich sulfides; and at 290 and 335 cm^?1 for troilite with, occasionally, an extra peak at 240 cm^?1. A peak at 160 cm^?1 is present in all Raman spectra and cannot be used to discriminate between the different sulfide compositions. According to group theory, none of the cubic monosulfides oldhamite, niningerite, or alabandite should present first‐order Raman spectra because of their ideal rocksalt structure. The occurrence of broad Raman peaks is tentatively explained by local breaking of symmetry rules. Measurements compare well with the infrared frequencies calculated from first‐principles calculations. Raman spectra arise from activation of certain vibrational modes due to clustering in the solid solutions or to coupling with electronic transitions in semiconductor sulfides.