A new titanium-bearing calcium aluminosilicate phase: I. Meteoritic occurrences and formation in synthetic systems

Abstract A new titanium-bearing calcium aluminosilicate mineral has been identified in coarse-grained calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites. The formula for this phase, which we have temporarily termed “UNK,” is Ca₃Ti(Al, Ti)₂(Si, Al)₃O¹⁴, and it is present in at least 8 of the 20 coarse-grained CAIs from the Allende CV3 chondrite examined as part of this project. The phase occurs in Types A and B1 inclusions as small tabular crystals oriented along two mutually perpendicular planes in melilite. UNK crystallizes from melts in dynamic crystallization experiments conducted in air from four bulk compositions modeled after Types A, B1, B2 and C inclusions. Cooling rates resulting in crystallization of UNK ranged from 0.5 to 200 °C/h from maximum (initial) temperatures of 1375 to 1580 °C. Only below 1190 °C does UNK itself begin to crystallize. To first order, the presence or absence of UNK from individual experiments can be understood in terms of the compositions of residual melts and nucleation probabilities. Compositions of synthetic and meteoritic UNK are very similar in terms of major oxides, differing only in the small amounts of trivalent Ti (7–13% of total Ti) in meteoritic samples. UNK crystallized from the Type A analog is similar texturally to that found in CAIs, although glass, which is typically associated with synthetic UNK, is not observed in meteoritic occurrences. A low Ti end-member of UNK (“Si-UNK”) with a composition near that of Ca₃Al₂Si₄O₁₄ was produced in a few samples from the Type B1 analog. This phase has not been found in the meteoritic inclusions.     

Red Wing Creek structure,North Dakota: Petrographical and geochemical studies,and confirmation of impact origin

Abstract The 9 km diameter Red Wing Creek structure, North Dakota, is located within the oil-rich Williston Basin at 47°36′N and 103°33′W. Earlier geophysical studies indicated that this subsurface structure has a central uplift, surrounded by an annular crater moat, and a raised rim. Breccias were encountered during drilling between ～2000 and 2800 m depth in the central uplift area, and the presence of shatter cone fragments in drill core samples was suggested to indicate an impact origin of the Red Wing Creek structure. We studied the petrographic and geochemical characteristics of samples of well cuttings from two boreholes at the center of the structure: the True Oil 22–27 Burlington Northern and True Oil 11–27 Burlington Northern wells. We found planar deformation features (PDFs) in quartz with up to three sets of different crystallographic orientations in sandstone- and siltstone-dominated samples from the True Oil 11–27 borehole. U-stage measurements of the crystallographic orientations of the PDFs showed the occurrence of the shock-characteristic (0001), and orientations, with a dominance of (0001) and orientations. The relative frequencies of the orientations indicate a shock pressure of at least 12–20 GPa. These results provide unambiguous evidence for shock metamorphism at Red Wing Creek and confirm that the structure was formed by impact.     

Vapor‐condensed phase processes in the early solar system

Abstract– Equilibrium thermodynamic calculations of the sequence of condensation of phases from a cooling gas of solar composition at total pressures thought to have prevailed in the inner part of the solar nebula successfully predict the primary mineral assemblages of refractory inclusions in CM2 and CV3 chondrites. Many refractory inclusions in CM2 chondrites contain a relatively SiO₂‐poor assemblage (spinel, hibonite, grossite, perovskite, corundum) that represents a high‐temperature stage of condensation, and some may be pristine condensates that escaped later melting. Compact Type A and Type B refractory inclusions, consisting of spinel, melilite, perovskite, Ca‐rich clinopyroxene ± anorthite, in CV3 chondrites are more SiO₂‐rich and equilibrated with the solar nebular gas at a slightly lower temperature. Textures of many of these objects indicate that they underwent melting after condensation, crystallizing into the same phase assemblage as their precursors. The Ti³⁺/Ti⁴⁺ ratio of their pyroxene indicates that this process occurred in a gas whose oxygen fugacity () was approximately 8.5 log units below that of the iron‐wüstite buffer, making them the only objects in chondrites known to have formed in a system whose composition was close to that of the sun. Relative to CI chondrites, these inclusions are uniformly enriched in a group of elements (e.g., Ca, REE, Zr, Ta, Ir) that are chemically diverse except for their high condensation temperatures in a system of solar composition. The enrichment factor, 17.5, can be interpreted to mean that these objects represent either the first 5.7 wt% of the condensable matter to condense during nebular cooling or the residue after vaporization of 94.3% of a CI chondrite precursor. The Mg and Si isotopic compositions of Types A and B inclusions are mass‐fractionated by up to 10 and 4 ‰/amu, respectively. When interpreted in terms of Rayleigh fractionation during evaporation of Mg and Si from the inclusions while they were molten, the isotopic compositions imply that up to 60% of the Mg and up to 25% of the Si were evaporated, and that approximately 80% of the enrichment in refractory (CaO+Al₂O₃) relative to more volatile (MgO+SiO₂) in the average inclusion is due to initial condensation and approximately 20% due to subsequent evaporation. The mineralogical composition, including the Ti³⁺/Ti⁴⁺ ratio of the pyroxene, in Inti, a particle sampled from Comet Wild 2 by the Stardust spacecraft, is nearly identical to that of a Type B inclusion, indicating that comets contain not only the lowest‐temperature condensates in the form of ices but the highest‐temperature condensates as well. The FeO/(FeO+MgO) ratios of olivine and pyroxene in the matrix and chondrules of carbonaceous and ordinary chondrites are too high to be made in a system of solar composition, requiring s only 1 or 2 log units below iron‐wüstite, more than 10⁵ times higher than that of a solar gas. Various ways have been devised to generate cosmic gases sufficiently oxidizing to stabilize significant FeO in olivine at temperatures above those where Fe‐Mg interdiffusion in olivine ceases. One is by vertical settling of dust toward the nebular midplane, enriching a region in dust relative to gas. Because dust is enriched in oxygen compared to carbon and hydrogen relative to solar composition, a higher results from total vaporization of the region, but the factor by which theoretical models have so far enriched the dust is 10 times too low. Another is by transporting icy bodies from the outer part of the nebula into the hot, inner part where vaporization of water ice occurs. Not only does this method fail to make the needed by a factor of 30–1000 but it also ignores simultaneous evaporation of carbon‐bearing ices that would make the even lower.     

Hydrothermal origin of hexagonal CaAl2Si2O8 (dmisteinbergite) in a compact type A CAI from the Northwest Africa 2086 CV3 chondrite

We report an occurrence of hexagonal CaAl₂Si₂O₈ (dmisteinbergite) in a compact type A calcium‐aluminum‐rich inclusion (CAI) from the CV3 (Vigarano‐like) carbonaceous chondrite Northwest Africa 2086. Dmisteinbergite occurs as approximately 10 μm long and few micrometer‐thick lath‐shaped crystal aggregates in altered parts of the CAI, and is associated with secondary nepheline, sodalite, Ti‐poor Al‐diopside, grossular, and Fe‐rich spinel. Spinel is the only primary CAI mineral that retained its original O‐isotope composition (Δ¹⁷O ~ ?24‰); Δ¹⁷O values of melilite, perovskite, and Al,Ti‐diopside range from ?3 to ?11‰, suggesting postcrystallization isotope exchange. Dmisteinbergite, anorthite, Ti‐poor Al‐diopside, and ferroan olivine have ¹⁶O‐poor compositions (Δ¹⁷O ~ ?3‰). We infer that dmisteinbergite, together with the other secondary minerals, formed by replacement of melilite as a result of fluid‐assisted thermal metamorphism experienced by the CV chondrite parent asteroid. Based on the textural appearance of dmisteinbergite in NWA 2086 and petrographic observations of altered CAIs from the Allende meteorite, we suggest that dmisteinbergite is a common secondary mineral in CAIs from the oxidized Allende‐like CV3 chondrites that has been previously misidentified as a secondary anorthite.     

Planar deformation features in quartz from impact‐produced polymict breccia of the Xiuyan crater,China

Abstract– The 1.8 km‐diameter Xiuyan crater is an impact structure in northeastern China, exposed in a Proterozoic metamorphic rock complex. The major rocks of the crater are composed of granulite, hornblendite, gneiss, tremolite marble, and marble. The bottom at the center of the crater covers about 100 m thick lacustrine sediments underlain by 188 m thick crater‐fill breccia. A layer of polymict breccia composed of clasts of granulite, gneiss, hornblendite, and fragments of glass as well as clastic matrix, occurs near the base, in the depth interval from 260 to 295 m. An investigation in quartz from the polymict breccia in the crater‐fill units reveals abundant planar deformation features (PDFs). Quartz with multiple sets of PDFs is found in clasts of granulite that consist of mainly quartz and feldspar, and in fine‐grained matrix of the impact‐produced polymict breccia. A universal stage was used to measure the orientation of PDFs in 70 grains of quartz from five thin sections made from the clasts of granulite of polymict breccia recovered at the depth of 290 m. Forty‐four percent of the quartz grains contain three sets of PDFs, and another 40% contain two sets of PDFs. The most abundant PDFs are rhombohedron forms of , , and with frequency of 33.5, 22.3, and 9.6%, respectively. A predominant PDF form of in quartz suggests a shock pressure >20 GPa. The occurrence of PDFs in quartz from the polymict breccia provides crucial evidence for shock metamorphism of target rocks and confirms the impact origin of this crater, which thus appears to be the first confirmed impact crater in China.     

Fine‐grained,spinel‐rich inclusions from the reduced CV chondrites Efremovka and Leoville: I. Mineralogy,petrology, and bulk chemistry

Abstract— Fine‐grained, spinel‐rich inclusions in the reduced CV chondrites Efremovka and Leoville consist of spinel, melilite, anorthite, Al‐diopside, and minor hibonite and perovskite; forsterite is very rare. Several CAIs are surrounded by forsterite‐rich accretionary rims. In contrast to heavily altered fine‐grained CAIs in the oxidized CV chondrite Allende, those in the reduced CVs experienced very little alteration (secondary nepheline and sodalite are rare). The Efremovka and Leoville fine‐grained CAIs are ¹⁶O‐enriched and, like their Allende counterparts, generally have volatility fractionated group II rare earth element patterns. Three out of 13 fine‐grained CAIs we studied are structurally uniform and consist of small concentrically zoned nodules having spinel ± hibonite ± perovskite cores surrounded by layers of melilite and Al‐diopside. Other fine‐grained CAIs show an overall structural zonation defined by modal mineralogy differences between the inclusion cores and mantles. The cores are melilite‐free and consist of tiny spinel ± hibonite ± perovskite grains surrounded by layers of anorthite and Al‐diopside. The mantles are calcium‐enriched, magnesium‐depleted and coarsergrained relative to the cores; they generally contain abundant melilite but have less spinel and anorthite than the cores. The bulk compositions of fine‐grained CAIs generally show significant fractionation of Al from Ca and Ti, with Ca and Ti being depleted relative to Al; they are similar to those of coarsegrained, type C igneous CAIs, and thus are reasonable candidate precursors for the latter. The finegrained CAIs originally formed as aggregates of spinel‐perovskite‐melilite ± hibonite gas‐solid condensates from a reservoir that was ¹⁶O‐enriched but depleted in the most refractory REEs. These aggregates later experienced low‐temperature gas‐solid nebular reactions with gaseous SiO and Mg to form Al‐diopside and ±anorthite. The zoned structures of many of the fine‐grained inclusions may be the result of subsequent reheating that resulted in the evaporative loss of SiO and Mg and the formation of melilite. The inferred multi‐stage formation history of fine‐grained inclusions in Efremovka and Leoville is consistent with a complex formation history of coarse‐grained CAIs in CV chondrites.     

Oxygen isotopic alteration in Ca‐Al‐rich inclusions from Efremovka: Nebular or parent body setting?

Abstract— In situ SIMS oxygen isotope data were collected from a coarse‐grained type B1 Ca‐Al‐rich inclusion (CAI) and an adjacent fine‐grained CAI in the reduced CV3 Efremovka to evaluate the timing of isotopic alteration of these two objects. The coarse‐grained CAI (CGI‐10) is a sub‐spherical object composed of elongate, euhedral, normally‐zoned melilite crystals ranging up to several hundreds of Pm in length, coarse‐grained anorthite and Al, Ti‐diopside (fassaite), all with finegrained (～10 μm across) inclusions of spinel. Similar to many previously examined coarse‐grained CAIs from CV chondrites, spinel and fassaite are ¹⁶O‐rich and melilite is ¹⁶O‐poor, but in contrast to many previous results, anorthite is ¹⁶O‐rich. Isotopic composition does not vary with textural setting in the CAI: analyses of melilite from the core and mantle and analyses from a variety of major element compositions yield consistent ¹⁶O‐poor compositions. CGI‐10 originated in an ¹⁶O‐rich environment, and subsequent alteration resulted in complete isotopic exchange in melilite. The fine‐grained CAI (FGI‐12) also preserves evidence of a 1st‐generation origin in an ¹⁶O‐rich setting but underwent less severe isotopic alteration. FGI‐12 is composed of spinel ± melilite nodules linked by a mass of Al‐diopside and minor forsterite along the CAI rim. All minerals are very fine‐grained (<5 μm) with no apparent igneous textures or zoning. Spinel, Al‐diopside, and forsterite are ¹⁶O‐rich, while melilite is variably depleted in ¹⁶O (δ^17,18O from ～‐40‰ to ?5‰). The contrast in isotopic distributions in CGI‐10 and FGI‐12 is opposite to the pattern that would result from simultaneous alteration: the object with finer‐grained melilite and a greater surface area/ volume has undergone less isotopic exchange than the coarser‐grained object. Thus, the two CAIs were altered in different settings. As the CAIs are adjacent to each other in the meteorite, isotopic exchange in CGI‐10 must have preceded incorporation of this CAI in the Efremovka parent body. This supports a nebular setting for isotopic alteration of the commonly observed ¹⁶O‐poor melilite in coarse‐grained CAIs from CV chondrites.     

The petrogenesis of type B1 Ca‐Al‐rich inclusions: The spinel perspective

Abstract— Minor element variations in MgAl₂O₄ spinel from the type B1 calcium‐aluminum‐rich inclusion (CAI) Allende TS‐34 confirm earlier studies in showing correlations between the minor element chemistry of spinels with their location within the inclusion and with the chemistry of host silicate phases. These correlations result from a combination of crystallization of a liquid produced by re‐melting event(s) and local re‐equilibration during subsolidus reheating. The correlation of the Ti and V in spinel inclusions with the Ti and V in the adjacent host clinopyroxene can be qualitatively explained by spinel and clinopyroxene crystallization prior to melilite, following a partial melting event. There are, however, difficulties in quantitative modeling of the observed trends, and it is easier to explain the Ti correlation in terms of complete re‐equilibration. The correlation of V in spinel inclusions with that in the adjacent host clinopyroxene also cannot be quantitatively modeled by fractional crystallization of the liquid produced by re‐melting, but it can be explained by partial re‐equilibration. The distinct V and Ti concentrations in spinel inclusions in melilite from the edge regions of the CAI are best explained as being affected by only a minor degree of re‐equilibration. The center melilites and included spinels formed during crystallization of the liquid produced by re‐melting, while the edge melilites and included spinels are primary. The oxygen isotope compositions of TS‐34 spinels are uniformly ¹⁶O‐rich, regardless of the host silicate phase or its location within the inclusion. Similar to other type B1 CAIs, clinopyroxene is ¹⁶O‐rich, but melilite is relatively ¹⁶O‐poor. These data require that the oxygen isotope exchange in TS‐34 melilite occurred subsequent to the last re‐melting event.     

Refractory calcium‐aluminum‐rich inclusions and aluminum‐diopside‐rich chondrules in the metal‐rich chondrites Hammadah al Hamra 237 and Queen Alexandra Range 94411

Abstract— The metal‐rich chondrites Hammadah al Hamra (HH) 237 and Queen Alexandra Range (QUE) 94411, paired with QUE 94627, contain relatively rare (<1 vol%) calcium‐aluminum‐rich inclusions (CAIs) and Al‐diopside‐rich chondrules. Forty CAIs and CAI fragments and seven Al‐diopside‐rich chondrules were identified in HH 237 and QUE 94411/94627. The CAIs, ～50–400 μm in apparent diameter, include (a) 22 (56%) pyroxene‐spinel ± melilite (+forsterite rim), (b) 11 (28%) forsterite‐bearing, pyroxene‐spinel ± melilite ± anorthite (+forsterite rim) (c) 2 (5%) grossite‐rich (+spinel‐melilite‐pyroxene rim), (d) 2 (5%) hibonite‐melilite (+spinel‐pyroxene ± forsterite rim), (e) 1 (2%) hibonite‐bearing, spinel‐perovskite (+melilite‐pyroxene rim), (f) 1 (2%) spinel‐melilite‐pyroxene‐anorthite, and (g) 1 (2%) amoeboid olivine aggregate. Each type of CAI is known to exist in other chondrite groups, but the high abundance of pyroxene‐spinel ± melilite CAIs with igneous textures and surrounded by a forsterite rim are unique features of HH 237 and QUE 94411/94627. Additionally, oxygen isotopes consistently show relatively heavy compositions with Δ¹⁷O ranging from ?6%0 to ?10%0 (1σ = 1.3%0) for all analyzed CAI minerals (grossite, hibonite, melilite, pyroxene, spinel). This suggests that the CAIs formed in a reservoir isotopically distinct from the reservoir(s) where “normal”, ¹⁶O‐rich (Δ¹⁷O < ?20%0) CAIs in most other chondritic meteorites formed. The Al‐diopside‐rich chondrules, which have previously been observed in CH chondrites and the unique carbonaceous chondrite Adelaide, contain Al‐diopside grains enclosing oriented inclusions of forsterite, and interstitial anorthitic mesostasis and Al‐rich, Ca‐poor pyroxene, occasionally enclosing spinel and forsterite. These chondrules are mineralogically similar to the Al‐rich barred‐olivine chondrules in HH 237 and QUE 94411/94627, but have lower Cr concentrations than the latter, indicating that they may have formed during the same chondrule‐forming event, but at slightly different ambient nebular temperatures. Aluminum‐diopside grains from two Al‐diopside‐rich chondrules have O‐isotopic compositions (Δ¹⁷O ? ?7 ± 1.1 %0) similar to CAI minerals, suggesting that they formed from an isotopically similar reservoir. The oxygen‐isotopic composition of one Ca, Al‐poor cryptocrystalline chondrule in QUE 94411/94627 was analyzed and found to have Δ¹⁷O ? ?3 ± 1.4%0. The characteristics of the CAIs in HH 237 and QUE 94411/94627 are inconsistent with an impact origin of these metal‐rich meteorites. Instead they suggest that the components in CB chondrites are pristine products of large‐scale, high‐temperature processes in the solar nebula and should be considered bona fide chondrites.     

A unique type B inclusion from Allende with evidence for multiple stages of melting

Abstract— A large (7 mm in diameter) Allende type B inclusion has a typical bulk composition and a unique structure: a fassaite‐rich mantle enclosing a melilite‐rich core. The core and mantle have sharply contrasting textures. In the mantle, coarse (?1 mm across), subhedral fassaite crystals enclose radially oriented melilite laths about 500 μm long that occur at the inclusion rim. The core consists of blocky melilite grains 20–50 μm across and poikilitically enclosed in anhedral fassaite grains that are optically continuous over ?1 mm. Another unique feature of this inclusion is that melilite laths also extend from the core into the mantle. Fassaite in both the core and mantle is very rich in fine‐grained (1–10 μm) spinel. The rim laths are normally zoned (Åk_30–70) inward from the rim of the inclusion with reverse zoning over the last ?200 μm to crystallize. A very wide range of melilite compositions is found in the core of the inclusion, where gehlenitic grains (Åk_5–12) occur. These grains are enclosed in strongly zoned (Åk_15–70) overgrowths. The gehlenitic cores and innermost parts of the overgrowths are Na₂O‐free, but the outer parts of the overgrowths are not. In the laths at the rim, Na₂O decreases inward from the rim, then increases. Fassaite in the core has the same range of Ti contents as that in the mantle: 2–9 wt% TiO₂ + Ti₂O₃. Two melting events are required to account for the features of this inclusion. In the first event, the precursor assemblage is heated to ?1400 °C and melts except for gehlenitic (Åk_5–12) melilite and some spinel. These grains become concentrated in the core. During cooling, Na₂O‐free melilite nucleates at the rim of the inclusion and on the relict grains in the core. After open system secondary alteration, the inclusion is heated again, but only to ?1260 °C. Melilite more gehlenitic than Åk₄₀ does not melt. During cooling, Na₂O‐bearing melilite crystallizes as small, blocky grains and laths in the core and as overgrowths on relict grains in the core and at the rim. Eventually melilite co‐crystallizes with fassaite, leading to the reverse zoning observed in the laths. The coexistence in this inclusion of Na‐free and Na‐bearing melilite, plus a positive correlation between Na₂O and åkermanite contents in melilite in an inclusion with a bulk Mg isotopic composition that is mass‐fractionated in favor of the heavy isotopes, are both consistent with at least two melting events. Several other recently described coarse‐grained inclusions also have features consistent with a sequence of early, high‐temperature melting, secondary alteration, and remelting at a lower temperature, suggesting that remelting of refractory inclusions was a common occurrence in the solar nebula.     

Al‐Mg systematics of hibonite‐bearing Ca,Al‐rich inclusions from Ningqiang

Abstract– Hibonite‐bearing Ca,Al‐rich inclusions (CAIs) usually occur in CM and CH chondrites and possess petrographic and isotopic characteristics distinctive from other typical CAIs. Despite their highly refractory nature, most hibonite‐bearing CAIs have little or no ²⁶Mg excess (the decay product of ²⁶Al), but do show wide variations of Ca and Ti isotopic anomalies. A few spinel‐hibonite spherules preserve evidence of live ²⁶Al with an inferred ²⁶Al/²⁷Al close to the canonical value. The bimodal distribution of ²⁶Al abundances in hibonite‐bearing CAIs has inspired several interpretations regarding the origin of short‐lived nuclides and the evolution of the solar nebula. Herein we show that hibonite‐bearing CAIs from Ningqiang, an ungrouped carbonaceous chondrite, also provide evidence for a bimodal distribution of ²⁶Al. Two hibonite aggregates and two hibonite‐pyroxene spherules show no ²⁶Mg excesses, corresponding to inferred ²⁶Al/²⁷Al < 8 × 10^?6. Two hibonite‐melilite spherules are indistinguishable from each other in terms of chemistry and mineralogy but have different Mg isotopic compositions. Hibonite and melilite in one of them display positive ²⁶Mg excesses (up to 25‰) that are correlated with Al/Mg with an inferred ²⁶Al/²⁷Al of (5.5 ± 0.6) × 10^?5. The other one contains normal Mg isotopes with an inferred ²⁶Al/²⁷Al < 3.4 × 10^?6. Hibonite in a hibonite‐spinel fragment displays large ²⁶Mg excesses (up to 38‰) that correlate with Al/Mg, with an inferred ²⁶Al/²⁷Al of (4.5 ± 0.8) × 10^?5. Prolonged formation duration and thermal alteration of hibonite‐bearing CAIs seem to be inconsistent with petrological and isotopic observations of Ningqiang. Our results support the theory of formation of ²⁶Al‐free/poor hibonite‐bearing CAIs prior to the injection of ²⁶Al into the solar nebula from a nearby stellar source.     

Beryllium‐boron and aluminum‐magnesium chronology of calcium‐aluminum‐rich inclusions in CV chondrites

Abstract— We have made Be‐B measurements in six calcium‐aluminum‐rich inclusions (CAIs) (mostly type B inclusions) from CV chondrites and compared them to Al‐Mg measurements. All CAIs show ¹⁰B excesses in melilite that are correlated with Be/B ratios. The initial ¹⁰Be/⁹Be ratio inferred from the correlation line is 6.2 times 10^?4. In contrast to the Be‐B system in melilite, the Al‐Mg system in anorthite is disturbed. This is probably due to B diffusion in melilite being slow compared with Mg diffusion in anorthite. This suggests that Be‐B chronology may be useful for measuring time differences of high‐temperature (melting, condensation, etc.) events in the early solar system.     

A new titanium-bearing calcium aluminosilicate phase: III. Crystals from a mixer furnace slag

Abstract Small crystals of an optically uniaxial Ti-bearing calcium aluminosilicate were discovered in a mixer furnace slag consisting mostly of åkermanitic melilite. The crystals have the same unit cell as those observed for a phase crystallized from slowly-cooled melts used to simulate the formation of aluminous inclusions in meteorites. Moreover, compositions of synthetic and meteoritic occurrences of the phase are all very similar and can be expressed in terms of a binary solid solution between the end-members Ca₃TiAl₂Si₃O₁₄ and Ca₃Ti(AlTi)(AlSi₂)O₁₄. Thus, crystallographic and crystallochemical information obtained from crystals in the mixer furnace slag can be used to constrain the origin of similar crystals found in meteoritic inclusions. We separated crystals from the mixer furnace slag by acid leaching; some were used for EPMA analysis, others were crushed for study by TEM methods or X-ray powder diffraction. Convergent beam electron diffraction shows that the crystals belong to the trigonal (rhombohedral) class and have point group symmetry 3m. X-ray powder diffraction gives the unit cell parameters a = 0.791 ± 0.009 nm, c = 0.492 ± 0.006 nm. The results suggest that the mineral has space group symmetry P3ml or P31m.     

Simultaneous measurements of Ca+ K,Ca+ H,Hα, Hβ, and He D3 emission in prominences

Simultaneously measured line intensities of Ca⁺ K and H, H, H and He D₃ are presented and compared with recent model calculations by Heasley and Milkey (1978). The model calculations are compatible with the observations. There is indication that the observed branching of the relation E(Ca⁺ K and H) E(H) depends on the widths of the Ca⁺-lines.     

On the abundance of calcium in the solar corona

Measured values for the total intensity of the continuum and the ratio of integrated intensities I( 5694)/I/(5446) are used to estimate the fraction of electrons along the line of sight contributing to the excitation of Caxv. This estimate of electron density along with an estimate of the dimension of the emitting region are used to find a value of the abundance of Ca in the solar corona. The estimated abundance is logN _Ca/N _H = -4.35.     

Nucleosynthesis of26Al in the early solar system and in cosmic rays

The nucleus²⁶Al(^1/2 = 7.4 × 10⁵ yr) has long been considered as a possible heat source during the formation of the solar system. Recent experimental work has found no evidence for²⁶Al at the time of final solidification of the meteorites. Due to the short half-life these measurements do not rule out the possibility that²⁶Al was a significant heat source a few million years prior to final solidification. For²⁶Al to be an effective heat source in the early solar system it is necessary for the ratio²⁶Al/Si to be 2×10^–7 at the time of a solidification. The nucleosynthetic yields of²⁶Al by silicon burning, carbon burning, and spallation are discussed. It is shown that²⁶Al can be synthesized in carbon and/or silicon-burning supernovae. However, time scales in the early solar system make it more likely that²⁶Al, if present in planets, was synthesized by a proton irradiation in the early solar system. An integrated proton flux >4×10¹⁸ cm^–2 is shown to be necessary in order for²⁶Al to be a significant heat source. No conclusive evidence has been observed for an irradiation of this magnitude. Therefore, unless such evidence is found, it should be assumed that²⁶Alwas not involved in the formation of the solar system. In addition, the production of²⁶Al in cosmic rays is discussed and it is shown that either resolution of the Al isotopes in the cosmic rays or accurate measurements of the variation with energy of the cosmic ray abundance ratios Al/Si and Mg/Si can be used to determine the age of the cosmic rays, _C.R.. Current abundance data are extremely uncertain; however, the trend tends toward values of _C.R. 10⁶ yr.Supported in part by the National Science Foundation [GP-19887, GP-28027, GP-27304].     

Extreme Ultraviolet Emission Lines of ca xv in Solar and Laboratory Spectra

New R-matrix calculations of electron impact excitation rates in Caxv are used to derive theoretical electron density diagnostic emission line intensity ratios involving 2s ²2p ²–2s2p ³ transitions, specifically R ₁=I(208.70 Å)/I(200.98 Å), R ₂=I(181.91 Å)/I(200.98 Å), and R ₃=I(215.38 Å)/I(200.98 Å), for a range of electron temperatures (T _e=10^6.4–10^6.8 K) and densities (N _e=10⁹–10¹³ cm^–3) appropriate to solar coronal plasmas. Electron densities deduced from the observed values of R ₁, R ₂, and R ₃ for several solar flares, measured from spectra obtained with the Naval Research Laboratory's S082A spectrograph on board Skylab, are found to be consistent. In addition, the derived electron densities are in excellent agreement with those determined from line ratios in Caxvi, which is formed at a similar electron temperature to Caxv. These results provide some experimental verification for the accuracy of the line ratio calculations, and hence the atomic data on which they are based. A set of eight theoretical Caxv line ratios involving 2s ²2p ²–2s2p ³ transitions in the wavelength range 140–216 Å are also found to be in good agreement with those measured from spectra of the TEXT tokamak plasma, for which the electron temperature and density have been independently determined. This provides additional support for the accuracy of the theoretical line ratios and atomic data.     

The stability of hibonite,melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

Abstract— Phase fields in which hibonite and silicate melt coexist with spinel, CaAl₄O₇, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al₂O₃-SiO₂-TiO₂ were determined. The hibonites contain up to 1.7 wt% SiO₂. For TiO₂, the experimentally determined partition coefficients between hibonite and coexisting melt, D^Hib/L_i, vary from 0.8 to 2.1 and generally decrease with increasing TiO₂ in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metastably from a melt Bulk compositions for all of these CAIs are consistent with an origin as melilite + hibonite + spinel + perovskite phase assemblages that were partially altered and in some cases partially or completely melted The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10^?3 atm, hibonite + corundum + vapor equilibrated at ～1260 °C and hibonite + spinel ± melilite + vapor at 1215 ± 10 °C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite ± corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical models for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu²⁺/Eu³⁺ decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect     

Formation of an unusual compact Type A refractory inclusion from Allende

Abstract— We report the results of a study of TS2, an unusual compact Type A inclusion from Allende. A distinctive, major feature of this inclusion is that many of its melilite crystals have no dominant core-rim zoning but instead consist of 50–200 μm patches of Mg-rich melilite (Åk_32–62, median Åk₅₁) set in or partially enclosed by, and optically continuous with, relatively Al-rich melilite (Åk_25–53, median Åk₃₈). The Al-rich regions have jagged, dendritic shapes but occur within crystals having straight grain boundaries. Another unusual feature of this inclusion is the size and spatial distribution of spinel. In many places, especially in the interior of the inclusion, the aluminous melilite encloses numerous, fine (0.5–5 μm) inclusions of spinel and minor perovskite and fassaite. The latter phases also occur as isolated grains throughout the inclusion. Coarse-grained spinel, ～50–150 μm across, occurs in clumps and chains enclosed in relatively Mg-rich melilite, whereas none of the fine spinel grains are clumped together. The sample also contains a spinel-free palisade body, 1.7 × 0.85 mm, that consists almost entirely of Åk-rich (45–65 mol%) melilite. Within the palisade body are two grains of perovskite with extremely Nb-rich (～4–8 wt% Nb₂O₅) cores and rims of typical composition. All phases in this inclusion have chondrite-normalized REE patterns that are consistent with crystal/melt partitioning superimposed upon a bulk modified Group II pattern. We suggest that TS2 had an anomalous cooling history and favor the following model for the formation of TS2. Precursors having a bulk modified Group II pattern melted. Rapid growth of large, dendritic, nonstoichiometric melilite crystals occurred. The melilite trapped pockets of melt and incorporated excess spinel components and TiO₂. Bubbles formed in the residual melt. As crystallization slowed, coarse spinel grew. Some spinel grains collected against bubbles, forming spherical shells, and others formed clumps and chains. Relatively Åk-rich melilite crystallized from the residual melt between dendritic melilite crystals and from melt trapped in pockets and between arms of dendrites, and incorporated the clumps and chains of coarse spinel. Bubbles broke and filled with late-stage melt, their shapes preserved by their spinel shells. Slow cooling, or perhaps an episode of reheating, allowed the early melilite to become stoichiometric by exsolving fine grains of spinel, perovskite and fassaite, and allowed the melilite to form smooth grain boundaries. Dendritic crystals are indicative of rapid growth and the melilite crystals in TS2 appear to be dendritic. Coarse, dendritic melilite crystals have been grown from Type B inclusion melts cooled at ～50–100 °C/h. If those results are applicable to Type A inclusions, we can make the first estimate of the cooling rate of a Type A inclusion, and it is outside the range (2–50 °C/h) generally inferred for Type B inclusions. The rapid cooling inferred here may be part of an anomalous thermal history for TS2, or it may be representative of part of a normal thermal history common to Types A and B that involved rapid cooling early (at high temperatures) as inferred for TS2, and slower cooling later (at lower temperatures), as inferred for Type B inclusions. We prefer the former explanation; otherwise, the unusual features of TS2 that are reported here would be common in Type A inclusions (which they are not).     

The forbidden line [Ca ii] λ7323 in the fraunhofer spectrum

New observations of the [Caii] 7323 Fraunhofer line are reported. The blending H₂O line was weak at the time of observation. Accurate estimates of the centre-limb variation of the equivalent width of the [Caii] transition are obtained and shown to be consistent with the calcium abundance log N(Ca) = 6.33.