Type C Ca, Al-rich inclusions from Allende: Evidence for multistage formation

The coarse-grained, igneous, anorthite-rich (Type C) CAIs from Allende studied (100, 160, 6-1-72, 3529-40, CG5, ABC, TS26, and 93) have diverse textures and mineralogies, suggesting complex nebular and asteroidal formation histories. CAIs 100, 160, 6-1-72, and 3529-40 consist of Al,Ti-diopside (fassaite; 13-23 wt% Al₂O₃, 2-14 wt% TiO₂), Na-bearing åkermanitic melilite (0.1-0.4 wt% Na₂O; Åk_30-75), spinel, and fine-grained (∼5-10 μm) anorthite groundmass. Most of the fassaite and melilite grains have “lacy” textures characterized by the presence of abundant rounded and prismatic inclusions of anorthite ∼5-10 μm in size. Lacy melilite is pseudomorphed to varying degrees by grossular, monticellite, and pure forsterite or wollastonite. CAI 6-1-72 contains a relict Type B CAI-like portion composed of polycrystalline gehlenitic melilite (Åk_10-40), fassaite, spinel, perovskite, and platinum-group element nuggets; the Type B-like material is overgrown by lacy melilite and fassaite. Some melilite and fassaite grains in CAIs 100 and 160 are texturally similar to those in the Type B portion of 6-1-72. CAIs ABC and TS26 contain relict chondrule fragments composed of forsteritic olivine and low-Ca pyroxene; CAI 93 is overgrown by a coarse-grained igneous rim of pigeonite, augite, and anorthitic plagioclase. These three CAIs contain very sodium-rich åkermanitic melilite (0.4-0.6 wt% Na₂O; Åk_63-74) and Cr-bearing Al,Ti-diopside (up to 1.6 wt% Cr₂O₃, 1-23 wt% Al₂O, 0.5-7 wt% TiO₂). Melilite and anorthite in the Allende Type C CAI peripheries are replaced by nepheline and sodalite, which are crosscut by andradite-bearing veins; spinel is enriched in FeO. The CAI fragment CG5 is texturally and mineralogically distinct from other Allende Type Cs. It is anorthite-poor and very rich in spinel poikilitically enclosed by Na-free gehlenitic melilite (Åk_20-30), fassaite, and anorthite; neither melilite nor pyroxene have lacy textures; secondary minerals are absent. The Al-rich chondrules 3655b-2 and 3510-7 contain aluminum-rich and ferromagnesian portions. The Al-rich portions consist of anorthitic plagioclase, Al-rich low-Ca pyroxene, and Cr-bearing spinel; the ferromagnesium portions consist of fosteritic olivine, low-Ca pyroxene, and opaque nodules.We conclude that Type C CAIs 100, 160, 6-1-72, and 3529-40 formed by melting of coarse-grained Type B-like CAIs which experienced either extensive replacement of melilite and spinel mainly by anorthite and diopside (traces of secondary Na-bearing minerals, e.g., nepheline or sodalite, might have formed as well), or addition of silica and sodium during the melting event. CG5 could have formed by melting of fine-grained spinel-melilite CAI with melilite and spinel partially replaced anorthite and diopside. CAIs ABC, 93, and TS-26 experienced melting in the chondrule-forming regions with addition of chondrule-like material, such as forsteritic olivine, low-Ca pyroxene, and high-Ca pyroxene. Anorthite-rich chondrules formed by melting of the Al-rich (Type C CAI-like) precursors mixed with ferromagnesian, Type I chondrule-like precursors. The Allende Type C CAIs and Al-rich chondrules experienced fluid-assisted thermal metamorphism, which resulted in pseudomorphic replacement of melilite and anorthite by grossular, monticellite, and forsterite (100, 160, 6-1-72, 3592-40) or by grossular, monticellite, and wollastonite (ABC, 93, TS-26). The pseudomorphic replacement was followed or accompanied by iron-alkali metasomatic alteration resulting in replacement of melilite and anorthite by nepheline and sodalite, enrichment of spinel in FeO, and precipitation of salite-hedenbergite pyroxenes, wollastonite, and andradite in fractures and pores in and around CAIs.     

“Fluffy” Type A Ca-, Al-rich inclusions in the Allende meteorite

Allende “fluffy” Type A's (FTA's) are a distinct sub-group of Ca-, Al-rich inclusions whose primary mineral assemblage consists of Al-rich melilite (Åk 0–33), spinel that is commonly very V-rich, perovskite and, frequently, hibonite. Some contain relatively coarse-grained melilite (up to 1.5 mm) that is intensely kink-banded and commonly reversely-zoned, hibonite and V-rich spinel. Others contain much finer-grained and strain-free melilite (?50 μm) and have not been found to contain hibonite or V-rich spinel. Some FTA's contain both coarser- and finer-grained melilite and textural relationships indicate that the latter is replacing the former. FTA's are characterized by extremely irregular shapes and 60–75 volume per cent of fine-grained, secondary alteration products. Many are aggregates of innumerable nodules, each of which is surrounded by a Wark-Lovering-type rim sequence. These nodules are frequently separated from one another by matrix-like clastic rim material. Other FTA's do not have nodular structure. Structural and mineralogical characteristics of their Wark-Lovering rims suggest that FTA's did not achieve their shapes by deformation of a liquid or a hot, plastic solid. In contrast to those in Type B inclusions, formation of reverse zoning in the coarser-grained melilite crystals in FTA's cannot be understood in terms of crystallization from a liquid but are readily explainable by condensation from a solar nebular gas during a period of falling pressure. Further evidence against a liquid origin is the wide range of spinel compositions within individual coarser-grained FTA's. The fact that the reversely-zoned melilite crystals cannot have been produced in any kind of sublimation or distillation process precludes formation of these inclusions as volatilization residues. FTA's are aggregates in some of which are preserved vapor-solid condensate grains that formed at high temperature in the solar nebula.     

Crystallization sequences of Ca-Al-rich inclusions from Allende: The effects of cooling rate and maximum temperature

We have studied the crystallization sequences, mineral chemistries, and textures that develop when an average Type B Ca-Al-rich inclusion composition is cooled in air from 1275–1580° C to below 1000°C at rates between 0.5 and 1000°C/hr. Crystallization sequences, the textures of all the major phases, pyroxene chemistry, and melilite zoning patterns are functions of both the cooling rate and the temperature from which cooling begins. Determination of the order of pyroxene and plagioclase crystallization has been identified as an important goal for petrographic studies of CAIs because it can be used to set constraints on the cooling rate experienced by an individual inclusion. Overall textures plus melilite zoning patterns and pyroxene chemistry can give important clues as to whether pyroxene or plagioclase began to crystallize first. Melilite texture and chemistry appear to yield the most valuable information on the maximum temperature to which an inclusion was raised prior to cooling.Comparison of our experimental results with petrographic observations of Type B CAIs suggests that most inclusions were partially melted and then cooled at rates on the order of a few tenths to tens of degrees per hour. Maximum temperatures of about 1400°C appear most likely for intermediate Type B Allende inclusions. Our results do not support the suggestion that the textures observed in these inclusions formed by crystallization of supercooled, metastable melt droplets condensed from nebular gas. The slow cooling rates we infer for CAIs are difficult to reconcile with models for their origin that imply simple radiative cooling of individual molten or partially molten droplets in a cold, low density environment. On the other hand, cooling rates of the nebular cloud are believed to have been much slower than those we have inferred for Type B CAIs. Scenarios that could be reconciled with the thermal history that we have inferred include drag heating of particles falling through nebular gas, heating by intense radiation (e.g., via flares) from the early sun, heating in nebular shock fronts, or other thermal heterogeneities in the early nebula allowing time scales for cooling (and heating) of CAIs much shorter than those for the nebular cloud as a whole. Successful models for the origin of Type B CAIs must account for the fact that most Type B CAIs cooled relatively slowly from a partially molten state.     

Crystallization sequences of Ca-Al-rich inclusions from Allende: An experimental study

The equilibrium crystallization sequence at 1 atmosphere in air of a melt corresponding in composition to the average composition of Type B Ca-Al-rich inclusions from the Allende meteorite is: spinel (1550°C) → melilite (1400°C; Åk22) → anorthite (1260°C) → Ti-Al-rich clinopyroxene (1230°C; “Ti-fassaite”). The melilite becomes increasingly åkermanitic with decreasing temperature. The pyroxene is similar in composition to fassaites from Type B inclusions. Preliminary results suggest that the crystallization sequence is similar at oxygen fugacities near the iron-wüstite buffer.The results of these experiments have been integrated with available phase equilibrium data in the system CaO-MgO-Al₂O₃-SiO₂TiO₂ and a phase diagram for predicting the crystallization sequences of liquids with compositions of coarse-grained Ca-Al-rich inclusions has been developed.Available bulk compositions of coarse-grained inclusions form a well-defined trend in terms of major elements, extending from Type A and Bl inclusions near the spinel-melilite join to more pyroxene-rich Type B2 inclusions. The trend deviates from the expected sequence of solid condensates from a nebular gas at P = 10^?3 atm if pure diopside is assumed to be the clinopyroxene that condenses. The Type A-B1 end of the trend is similar in composition to calculated equilibrium condensates at 1202–1227°C and the trend as a whole parallels the sequence of condensates expected from diopside condensation at ~ 1170°C. The trend is consistent to first order with the condensation of solid Ti-rich fassaite in place of pure diopside at higher temperatures than those at which pure diopside is predicted to condense. Partially molten condensates may be likely in this case or if the nebular pressure is higher than 10^?3 atm.     

Origin of compact type A refractory inclusions from CV3 carbonaceous chondrites

Compact type A (CTA) inclusions are one of the major types of coarse-grained refractory inclusions found in carbonaceous chondrites. They have not been studied in a systematic fashion, leading to some uncertainties and unproven assumptions about their origin. To address this situation, we studied a total of eight CTAs from Allende, Efremovka and Axtell by scanning electron-microscopic and electron and ion-microprobe techniques. These inclusions are very melilite-rich, ranging from ∼60 vol% to nearly monomineralic. Also present are Mg–Al spinel (5–20%), perovskite (trace–∼3%) and, in some samples, Ti-rich (∼17 wt% TiO₂^tot) fassaite (trace–∼20%), and rhönite (≤1%). Melilite compositions are mostly between Åk₁₅ and Åk₄₀. Chondrite-normalized REE abundance patterns for melilite (flat at ∼10 × CI with positive Eu anomalies) and fassaite (slight HREE enrichment relative to LREE and negative Eu anomalies) are like those for their counterparts in once-molten type B inclusions. The patterns for rhönite have positive slopes from La through Lu and abundances <10 × CI for La and 35–60 × CI for Lu. Features of CTAs that suggest that they were once molten include: rounded inclusion shapes; positively correlated Sc and V abundances in fassaite; radially oriented melilite laths at inclusion rims; and the distribution of trace elements among the phases. Fractional crystallization models show that, with one exception, the REE contents of perovskite and fassaite arose by crystallization of these phases from late, residual liquids that would have resulted from prior crystallization of the observed proportions of melilite and spinel from liquids having the bulk compositions of the inclusions. One Allende CTA (TS32), however, has several features (irregular shape, reversely zoned melilite, fassaite REE contents) that are not readily explained by crystallization from a melt. This inclusion may have undergone little melting and may be dominated by relict grains.     

Origin of low-Ca pyroxene in amoeboid olivine aggregates: Evidence from oxygen isotopic compositions

Amoeboid olivine aggregates (AOAs) in primitive carbonaceous chondrites consist of forsterite (Fa_<2), Fe,Ni-metal, spinel, Al-diopside, anorthite, and rare gehlenitic melilite (Åk_<15). ∼10% of AOAs contain low-Ca pyroxene (Fs_1-3Wo_1-5) that is in corrosion relationship with forsterite and is found in three major textural occurrences: (i) thin (<15 μm) discontinuous layers around forsterite grains or along forsterite grain boundaries in AOA peripheries; (ii) 5-10-μm-thick haloes and subhedral grains around Fe,Ni-metal nodules in AOA peripheries, and (iii) shells of variable thickness (up to 70 μm), commonly with abundant tiny (3-5 μm) inclusions of Fe,Ni-metal grains, around AOAs. AOAs with the low-Ca pyroxene shells are compact and contain euhedral grains of Al-diopside surrounded by anorthite, suggesting small (10%-20%) degree of melting. AOAs with other textural occurrences of low-Ca pyroxene are rather porous. Forsterite grains in AOAs with low-Ca pyroxene have generally ¹⁶O-rich isotopic compositions (Δ¹⁷O < −20‰). Low-Ca pyroxenes of the textural occurrences (i) and (ii) are ¹⁶O-enriched (Δ¹⁷O < −20‰), whereas those of (iii) are ¹⁶O-depleted (Δ¹⁷O = −6‰ to −4‰). One of the extensively melted (>50%) objects is texturally and mineralogically intermediate between AOAs and Al-rich chondrules. It consists of euhedral forsterite grains, pigeonite, augite, anorthitic mesostasis, abundant anhedral spinel grains, and minor Fe,Ni-metal; it is surrounded by a coarse-grained igneous rim largely composed of low-Ca pyroxene with abundant Fe,Ni-metal-sulfide nodules. The mineralogical observations suggest that only spinel grains in this igneous object were not melted. The spinel is ¹⁶O-rich (Δ¹⁷O ∼ −22‰), whereas the neighboring plagioclase mesostasis is ¹⁶O-depleted (Δ¹⁷O ∼ −11‰).We conclude that AOAs are aggregates of solar nebular condensates (forsterite, Fe,Ni-metal, and CAIs composed of Al-diopside, anorthite, spinel, and ±melilite) formed in an ¹⁶O-rich gaseous reservoir, probably CAI-forming region(s). Solid or incipiently melted forsterite in some AOAs reacted with gaseous SiO in the same nebular region to form low-Ca pyroxene. Some other AOAs appear to have accreted ¹⁶O-poor pyroxene-normative dust and experienced varying degrees of melting, most likely in chondrule-forming region(s). The most extensively melted AOAs experienced oxygen isotope exchange with ¹⁶O-poor nebular gas and may have been transformed into chondrules. The original ¹⁶O-rich signature of the precursor materials of such chondrules is preserved only in incompletely melted grains.     

Mineralogy and petrology of Al-rich objects and amoeboid olivine aggregates in the CH carbonaceous chondrite North West Africa 739

The aluminum-rich (>10 wt% Al₂O₃) objects in the CH carbonaceous chondrite North West Africa (NWA) 739 include Ca,Al-rich inclusions (CAIs), Al-rich chondrules, and isolated mineral grains (spinel, plagioclase, glass). Based on the major mineralogy, 54 refractory inclusions found in about 1 cm² polished section of NWA 739 can be divided into hibonite-rich (16%), grossite-rich (26%), melilite-rich (28%), spinel-pyroxene-rich (16%) CAIs, and amoeboid olivine aggregates, (AOA's, 17%). Most CAIs are rounded, 25–185 μm (average=70 μm) in apparent diameter, contain abundant, tiny perovskite grains, and typically surrounded by a single- or double-layered rim composed of melilite and/or Al-diopside; occasionally, layers of spinel+hibonite and forsterite are observed. The AOAs are irregularly shaped, 100–250 μm (average=175 μm) in size, and consist of forsterite, Fe,Ni-metal, and CAIs composed of Al-diopside, anorthite, and minor spinel. One AOA contains compact, rounded melilite-spinel-perovskite CAIs and low-Ca pyroxene replacing forsterite. The Al-rich (>10 wt% bulk Al₂O₃) chondrules are divided into Al-diopside-rich and plagioclase-rich. The Al-diopside-rich chondrules, 50–310 μm (average=165 μm) in apparent diameter, consist of Al-diopside, skeletal forsterite, spinel, ±Al-rich low-Ca pyroxene, and ±mesostasis. The plagioclase-rich chondrules, 120–455 μm (average=285 μm) in apparent diameter, are composed of low-Ca and high-Ca pyroxenes, forsterite, anorthitic plagioclase, Fe,Ni-metal nodules, and mesostasis. The isolated spinel occurs as coarse, 50–125 μm in size, subhedral grains, which are probably the fragments of Al-diopside chondrules. The isolated plagioclase grains are too coarse (60–120 μm) to have been produced by disintegration of chondrules or CAIs; they range in composition from nearly pure anorthite to nearly pure albite; their origin is unclear. The Al-rich objects show no evidence for Fe-alkali metasomatic or aqueous alteration; the only exception is an Al-rich chondrule fragment with anorthite replaced by nepheline. They are texturally and mineralogically similar to those in other CH chondrites studied (Acfer 182, ALH85085, PAT91467, NWA 770), but are distinct from the Al-rich objects in other chondrite groups (CM, CO, CR, CV). The CH CAIs are dominated by very refractory minerals, such as hibonite, grossite, perovskite and gehlenitic melilite, and appear to have experienced very low degrees of high-temperature alteration reactions. These include replacement of grossite by melilite, of melilite by anorthite, diopside, and spinel, and of forsterite by low-Ca pyroxene. Only a few CAIs show evidence for melting and multilayered Wark-Lovering rims. These observations may suggest that CH CAIs experienced rather simple formation history and escaped extensive recycling. In order to preserve the high-temperature mineral assemblages, they must have been efficiently isolated from the hot nebular region, like some chondrules and the zoned Fe,Ni-metal grains in CH chondrites.     

The mineral chemistry and origin of inclusion matrix and meteorite matrix in the Allende CV3 chondrite

The two textural varieties of olivine-rich Allende inclusions (rimmed and unrimmed olivine aggregates) consist primarily of a porous, fine-grained mafic constituent (inclusion matrix) that differs from the opaque meteorite matrix of CV3 chondrites by being relatively depleted in sulfides, metal grains, and (perhaps) carbonaceous material. Olivine is the most abundant mineral in Allende inclusion matrix; clinopyroxene, nepheline, sodalite, and Ti-Al-pyroxene occur in lesser amounts. Olivine in unrimmed olivine aggregates (Type 1A inclusions) is ferrous and has a narrow compositional range (Fo_50–65). Olivine in rimmed olivine aggregates (Type 1B inclusions) is, on average, more magnesian, with a wider compositional range (Fo_53–96). Olivine grains in the granular rims of Type 1B inclusions are zoned, with magnesian cores (Fo_>80) and ferrous rinds (Fo_<70). Ferrous olivines (Fo_<65) in both varieties of inclusions commonly contain significant amounts of Al₂O₃ (as much as ~0.7 wt%), CaO (as much as ~0.4 wt%), and TiO₂ (as much as ~0.2 wt%), refractory elements that probably occur in submicroscopic inclusions of Ca,Al,Ti-rich glass (rather than in the olivine crystal structure). Defocussed beam analyses of Allende matrix materials demonstrate that: (1) inclusion matrix in Type 1A inclusions is more enriched in olivine and FeO than inclusion matrix in the cores of Type 1B inclusions; (2) opaque matrix materials are depleted in feldspathoids and enriched in sulfides and metal grains relative to inclusion matrix; (3) the bulk compositions of Type 1A and Type 1B inclusions overlap; and (4) excluding sulfides and metal, the bulk compositions of Allende matrix materials cluster in a complementary pattern around the bulk composition of C1 chondrites.Inclusion matrix and meteorite matrix in Allende and other CV3 chondrites are probably relatively primitive nebular material, but a careful evaluation of the equilibrium condensation model suggests that these matrix materials do not consist of crystalline phases that formed under equilibrium conditions in a relatively cool gas of solar composition. Allende inclusion matrix is interpreted as an aggregate of condensates that formed under relatively oxidizing, non-equilibrium conditions from supercooled, supersaturated vapors produced during the vaporization of interstellar dust by aerodynamic drag heating in the solar nebula; CV3 meteorite matrix contains, in addition, a proportion of interstellar material that was heated (but not vaporized) in the nebula. Granular olivine in rimmed olivine aggregates may have formed during the recrystallization and incipient melting of aggregates of inclusion matrix in the nebula. The mineral chemistry of matrix olivine in Allende seems to have been established by three different processes: non-equilibrium vapor → solid condensation; recrystallization and partial melting in the nebula; and $\text{Fe}\text{Mg}$ equilibration (without textural homogenization) in the meteorite parent body.     

Formation of refractory inclusions by evaporation of condensate precursors

Berman’s (1983) activity-composition model for CaO-MgO-Al₂O₃-SiO₂ liquids is used to calculate the change in bulk chemical and isotopic composition during simultaneous cooling, evaporation, and crystallization of droplets having the compositions of reasonable condensate precursors of Types A and B refractory inclusions in CV3 chondrites. The degree of evaporation of MgO and SiO₂, calculated to be faithfully recorded in chemical and isotopic zoning of individual melilite crystals, is directly proportional to evaporation rate, which is a sensitive function of P_H2, and inversely proportional to the droplet radius and cooling rate. When the precursors are partially melted in pure hydrogen at peak temperatures in the vicinity of the initial crystallization temperature of melilite, their bulk chemical compositions evolve into the composition fields of refractory inclusions, mass-fractionated isotopic compositions of Mg, Si, and O are produced that are in the range of the isotopic compositions of natural inclusions, and melilite zoning profiles result that are similar to those observed in real inclusions. For droplets of radius 0.25 cm evaporating at P_H2 = 10⁻⁶ bar, precursors containing 8 to 13 wt.% MgO and 20 to 23% SiO₂ evolve into objects similar to compact Type A inclusions at cooling rates of 2 to 12 K/h, depending on the precise starting composition. Precursors containing 13 to 14 wt.% MgO and 23 to 26% SiO₂ evolve into objects with the characteristics of Type B1 inclusions at cooling rates of 1.5 to 3 K/h. The relatively SiO₂-poor members of the Type B2 group can be produced from precursors containing 14 to 16 wt.% MgO and 27 to 33% SiO₂ at cooling rates of <1 K/h. Type B2’s containing 27 to 35 wt.% SiO₂ and <12% MgO require precursors with higher SiO₂/MgO ratios at MgO > 15% than are found on any condensation curve. The characteristics of fluffy Type A inclusions, including their reversely zoned melilite, can only be understood in the context of this model if they contain relict melilite.     

Melt inclusions in olivine and pyroxene phenocrysts from lamprophyres of Chhaktalao Area,Madhya Pradesh,India

Melt inclusions in olivine and pyroxene phenocrysts in kersantite and camptonite at Chhaktalao in Madhya Pradesh, India are mainly of the evolved type forming daughter minerals of olivine, pyroxene, plagioclase, spinel, mica, titanomagnetite and sulphides. Heating studies exhibit a temperature range from 1215° to 1245°C for the melt inclusions in olivine in camptonite and 1220–1245°C for olivine in kersantite. The temperature for melt inclusions in pyroxene ranged from 1000° to 1150°C in camptonite and 850–1100°C for pyroxene in kersantite. The bubble inside these melt inclusions is mainly CO₂. The T_h°C of CO₂ into liquid phase occurred between 26° and 31°C in olivine and 25–30°C in pyroxene from kersantite and camptonite. The maximum density estimated is 0.72 g/cm³ and the minimum is 0.45 g/cm³. The depth of entrapment of the melt inclusion is estimated between 10–15 km. The pressure of entrapment of melt inclusion in olvine is 4.6 kbar where as that in pyroxene is 3.7 kbar. The lamprophyres in the Chhaktalao area are considered to be derived from low depth and low pressure region, possibly within spinel lherzolite zone.     

Amoeboid olivine aggregates with low-Ca pyroxenes: a genetic link between refractory inclusions and chondrules?

Amoeboid olivine aggregates (AOAs) in primitive (unmetamorphosed and unaltered) carbonaceous chondrites are uniformly ¹⁶O-enriched (Δ¹⁷O ∼ −20‰) and consist of forsterite (Fa_<2), FeNi-metal, and a refractory component (individual CAIs and fine-grained minerals interspersed with forsterite grains) composed of Al-diopside, anorthite, ±spinel, and exceptionally rare melilite (Åk_<15); some CAIs in AOAs have compact, igneous textures. Melilite in AOAs is replaced by a fine-grained mixture of spinel, Al-diopside, and anorthite. Spinel is corroded by anorthite or by Al-diopside. In ∼10% of > 500 AOAs studied in the CR, CV, CM, CO, CH, CB, and ungrouped carbonaceous chondrites Acfer 094, Adelaide, and LEW85332, forsterite is replaced to a various degree by low-Ca pyroxene. There are three major textural occurrences of low-Ca pyroxene in AOAs: (i) thin (<10 μm) discontinuous layers around forsterite grains or along forsterite grain boundaries in AOA peripheries; (ii) haloes and subhedral grains around FeNi-metal nodules in AOA peripheries, and (iii) thick (up to 70 μm) continuous layers with abundant tiny inclusions of FeNi-metal grains around AOAs. AOAs with low-Ca pyroxene appear to have experienced melting of various degrees. In the most extensively melted AOA in the CV chondrite Leoville, only spinel grains are relict; forsterite, anorthite and Al-diopside were melted. This AOA has an igneous rim of low-Ca pyroxene with abundant FeNi-metal nodules and is texturally similar to Type I chondrules.Based on these observations and thermodynamic analysis, we conclude that AOAs are aggregates of relatively low temperature solar nebular condensates originated in ¹⁶O-rich gaseous reservoir(s), probably CAI-forming region(s). Some of the CAIs were melted before aggregation into AOAs. Many AOAs must have also experienced melting, but of a much smaller degree than chondrules. Before and possibly after aggregation, melilite and spinel reacted with the gaseous SiO and Mg to form Ca-Tschermakite (CaAl₂SiO₆)-diopside (CaMgSi₂O₆) solid solution and anorthite. Solid or incipiently melted olivine in some AOAs reacted with gaseous SiO in the CAI- or chondrule-forming regions to form low-Ca pyroxene: Mg₂SiO₄ + SiO_(g) + H₂O_(g) = Mg₂Si₂O₆ + H_2(g). Some low-Ca pyroxenes in AOAs may have formed by oxidation of Si-bearing FeNi-metal: Mg₂SiO₄ + Si_{(in FeNi)} + 2H₂O_(g) = Mg₂Si₂O₆ + 2H_2(g) and by direct gas-solid condensation: Mg_(g) + SiO_(g) +H₂O_(g) = Mg₂Si₂O_6(s) + H_2(g) from fractionated (Mg/Si ratio < solar) nebular gas.Although bulk compositions of AOAs are rather similar to those of Type I chondrules, on the projection from spinel onto the plane Ca₂SiO₄-Mg₂SiO₄-Al₂O₃, these objects plot on different sides of the anorthite-forsterite thermal divide, suggesting that Type I chondrules cannot be produced from AOAs by an igneous fractionation. Formation of low-Ca pyroxene by reaction of AOAs with gaseous SiO and by melting of silica-rich dust accreted around AOAs moves bulk compositions of the AOAs towards chondrules, and provide possible mechanisms of transformation of refractory materials into chondrules or chondrule precursors. The rare occurrences of low-Ca pyroxene in AOAs may indicate that either AOAs were isolated from the hot nebular gas before condensation of low-Ca pyroxene or that condensation of low-Ca pyroxene by reaction between forsterite and gaseous SiO was kinetically inhibited. If the latter is correct, then the common occurrences of pyroxene-rich Type I chondrules may require either direct condensation of low-Ca pyroxenes or SiO₂ from fractionated nebular gas or condensation of gaseous SiO into chondrule melts.     

Ca-Al-rich inclusions from the Ningqiang meteorite: continuous assemblages of nebular condensates and genetic link to Type B inclusions

The petrography and mineral chemistry of 110 Ca-, Al-rich inclusions (CAIs) and 9 Ca- and/or Al-rich amoeboid olivine aggregates (AOAs) from the Ningqiang carbonaceous chondrite are reported. These CAIs are referred to as hibonite-bearing and hibonite-free melilite-spinel-rich (Type A), and spinel-pyroxene inclusions. Melilite is more gehlenitic in the hibonite-bearing Type As than in the other two types, and all of them vary within a range of Åk_0-30. Modal compositions of the three types of CAIs overlap with each other, and make up a continuum with wide ranges of melilite: spinel: diopside. The diopside occurs as rims on the CAIs or their individual concentric objects. The 9 AOAs contain spinel ± diopside ± anorthite in the centers of the aggregates; the spinel grains rimmed by diopside in the centers are similar to the spinel-pyroxene inclusions. Bulk compositions of these CAIs vary along the condensation trajectory, with the hibonite-bearing Type As plotting at the beginning followed by hibonite-free Type As then by spinel-pyroxene inclusions as temperature decreases. Bulk compositions of the AOAs are close to the lowest temperature condensation trajectory. Except for a few with compact textures, most of the Type As and spinel-pyroxene inclusions are fluffy aggregates, probably pristine vapor-solid condensates of the nebula.The bulk compositions of the Type As appear to overlap with the range of most melilite-Ti-Al-clinopyroxene-rich (Type B) inclusions. Hence, crystallization of liquids produced by melting the Type As can form Type B inclusions, without significant evaporative loss of MgO or SiO₂. A few Type Bs have bulk compositions deviating from the range of their proposed precursors, and may have suffered significant evaporation, as suggested in previous studies.     

Fluid inclusions as petrogenetic indicators in granulite xenoliths,Pali-Aike volcanic field,Chile

Granulite xenoliths within alkali olivine basalts of the Pali-Aike volcanic field, southern Chile, contain the mineral assemblage orthopyroxene + clinopyroxene + plagioclase + olivine + green spinel. These granulites are thought to be accidental inclusions of the lower crust incorporated in the mantle-derived basalt during its rise to the surface. Symplectic intergrowths of pyroxene and spinel developed between olivine and plagioclase imply that the reaction olivine+plagioclase = Al-orthopyroxene + Al-clinopyroxene + spinel (1) occurred during subsolidus cooling and recrystallization of a gabbroic protolith of the granulites.Examination of fluid inclusions in the granulites indicates the ubiquitous presence of an essentially pure CO₂ fluid phase. Inclusions of three different parageneses have been recognized: Type I inclusions occur along exsolution lamellae in clinopyroxene and are thought to represent precipitation of structurally-bound C or CO₂ during cooling of the gabbro. These are considered the most primary inclusions present. Type II inclusions occur as evenly distributed clusters not associated with any fractures. These inclusions probably represent entrapment of a free fluid phase during recrystallization of the host grains. IIa inclusions are found in granoblastic grains and have densities of 0.68–0.88 g/cm³. Higher density (=0.90–1.02 g/cm³) IIb inclusions occur only in symplectite phases. Secondary Type III CO₂+glass inclusions with =0.47–0.78 g/cm³ occur along healed fractures where basalt has penetrated the xenoliths. Type III inclusions appear related to exsolution of CO₂ from the host basalt during its ascent to the surface. These data suggest that CO₂ is an important constituent of the lower crust under conditions of granulite facies metamorphism, indicated by Type I and II fluid inclusions, and of the mantle, as indicated by Type III inclusions.Correlation of fluid inclusion densities with P-T conditions calculated from both two-pyroxene geothermometry and reation (1) indicate emplacement of a gabbroic pluton at 1,200–1,300° C, 4–6 kb; cooling was accompanied by a slight increase in pressure due to crustal thickening, and symplectite formation occurred at 850±35° C, 5–7 kb. Capture of the xenoliths by the basalt resulted in heating of the granulites, and CO₂ from the basalt was continuously entrapped by the xenoliths over the range 1,000–1,200° C, 4–6 kb. Examination of fluid inclusions of different generations can thus be used in conjunction with other petrologic data to place tight constraints on the specific P-T path followed by the granulite suite, in addition to indicating the nature of the fluid phase present at depth.     

Two forsterite-bearing FUN inclusions in the Allende meteorite

We have discovered two FUN inclusions, CG-14 and TE, among a group of five forsterite-rich inclusions in Allende, two of which are described for the first time herein. All five consist of euhedral forsterite and spinel crystals poikilitically enclosed by fassaite. Forsterite and spinel are usually segregated from one another, sometimes into a spinel-rich mantle and a forsterite-rich core. Some inclusions contain vesicles, indicating that they were once molten. The crystallization sequence inferred from textures is: spinel, forsterite, fassaite and, finally, Mg-rich melilite. One concentrically-zoned inclusion contains melilite in its mantle whose composition lies on the opposite side of the liquidus minimum in the melilite binary from that in its core. This suggests that segregation of forsterite from spinel in all of these inclusions could be due to volatilization of MgO and SiO₂ relative to Al₂O₃ and CaO from the outsides of droplets. CG-14 is relatively uniformly enriched in refractory elements relative to Cl chondrites by a factor similar to that for Ca-, Al-rich coarse-grained inclusions except for Ca, Al and Hf which are unusually low. No Ce anomaly such as found in FUN inclusions Cl and HAL is present in CG-14. Whole-rock samples of CG-14 and TE are more strongly mass-fractionated in oxygen relative to “normal” Allende inclusions than the FUN inclusion EK 1-4-1 and less so than Cl. Relative to bulk Allende, both inclusions have strongly massfractionated magnesium and silicon and ²⁵Mg excesses or deficits of ²⁴Mg or ²⁶Mg. CG-14 has a ²⁹Si excess or a deficit of ²⁸Si or ³⁰Si. Volatilization loss cannot be responsible for the magnesium and silicon isotope fractionations, as this would require prohibitively large mass loss from these magnesium-rich inclusions. The remarkable similarity in textures between FUN and non-FUN inclusions implies similar thermal histories, arguing against different rates of evaporative loss of major elements. Sputtering alone may be insufficient to account for the magnitude and direction of oxygen isotope fractionation in FUN inclusions.     

The I-Xe record of alteration in the allende CV chondrite

Complex I-Xe and mineralogical studies have been performed on four heavily-altered Allende fine-grained spinel-rich Ca, Al-rich inclusions (CAIs) and four Allende dark inclusions (DIs) showing various degrees of iron-alkali metasomatic alteration. The CAIs are largely composed of Fe-rich spinel, Al-diopside, and secondary nepheline and sodalite. The DIs consist of chondrules and Allende-like matrix composed of lath-shaped fayalitic olivine, nepheline, sodalite, and Ca, Fe-rich pyroxene ± andradite ± FeNi-sulfide nodules. Chondrule phenocrysts are extensively or completely replaced by fayalitic olivine, nepheline, and sodalite; metal nodules are replaced by FeNi-sulfides, andradite and Ca, Fe-rich pyroxenes. The chondrules and matrices are crosscut by Ca, Fe-rich pyroxene ± FeNi-sulfide ± fayalitic olivine veins. DIs are surrounded by continuous Ca-rich rims composed of andradite, wollastonite, kirschsteinite, and Ca, Fe-rich pyroxenes, whereas the outer portions of the inclusions are depleted in Ca.Three CAIs yield well-defined I-Xe isochrons with ages 3.1 ± 0.2, 3.0 ± 0.2 and 3.7 ± 0.2 Ma younger than the Shallowater internal standard (4566 ± 2 Ma). Similar release profiles suggest the same iodine carrier (most probably sodalite) for all four CAIs. The Allende DIs yield I-Xe ages from 0.8 ± 0.3 to 1.9 ± 0.2 Ma older than Shallowater. Based on the petrographic observations, we infer that the DIs experienced at least two-stage alteration. During an early stage of the alteration, which took place in an asteroidal setting, but not in the current location of the DIs, chondrule silicates were replaced by secondary fayalitic olivine, nepheline, and sodalite. Calcium lost from the chondrules was redeposited as Ca, Fe-rich pyroxene veins and Ca, Fe-rich pyroxene ± andradite nodules in the matrix. The second stage of alteration resulted in mobilization of Ca from the DIs and its re-deposition as Ca-rich rims composed of Ca, Fe-rich pyroxenes, andradite, and wollastonite, around the DIs. We interpret I-Xe ages of the DIs as time of their alteration prior incorporation into Allende. The younger I-Xe ages of the fine-grained spinel-rich CAIs may reflect hydrothermal alteration of the Allende host, which could have occurred contemporaneously with the second stage of alteration of the Allende DIs. The lack of evidence for the disturbance of I-Xe system in the Allende DIs may suggest that fluid responsible for the alteration of the Allende CAIs was in equilibrium with the I- and Xe-bearing phases of the DIs.     

Amoeboid olivine aggregates and related objects in carbonaceous chondrites: records of nebular and asteroid processes

Amoeboid olivine aggregates (AOAs) are the most common type of refractory inclusions in CM, CR, CH, CV, CO, and ungrouped carbonaceous chondrites Acfer 094 and Adelaide; only one AOA was found in the CB_b chondrite Hammadah al Hamra 237 and none were observed in the CB_a chondrites Bencubbin, Gujba, and Weatherford. In primitive (unaltered and unmetamorphosed) carbonaceous chondrites, AOAs consist of forsterite (Fa_<2), Fe, Ni-metal (5-12 wt% Ni), and Ca, Al-rich inclusions (CAIs) composed of Al-diopside, spinel, anorthite, and very rare melilite. Melilite is typically replaced by a fine-grained mixture of spinel, Al-diopside, and ±anorthite; spinel is replaced by anorthite. About 10% of AOAs contain low-Ca pyroxene replacing forsterite. Forsterite and spinel are always ¹⁶O-rich (δ^17,18O∼−40‰ to −50‰), whereas melilite, anorthite, and diopside could be either similarly ¹⁶O-rich or ¹⁶O-depleted to varying degrees; the latter is common in AOAs from altered and metamorphosed carbonaceous chondrites such as some CVs and COs. Low-Ca pyroxene is either ¹⁶O-rich (δ^17,18O∼−40‰) or ¹⁶O-poor (δ^17,18O∼0‰). Most AOAs in CV chondrites have unfractionated (∼2-10×CI) rare-earth element patterns. AOAs have similar textures, mineralogy and oxygen isotopic compositions to those of forsterite-rich accretionary rims surrounding different types of CAIs (compact and fluffy Type A, Type B, and fine-grained, spinel-rich) in CV and CR chondrites. AOAs in primitive carbonaceous chondrites show no evidence for alteration and thermal metamorphism. Secondary minerals in AOAs from CR, CM, and CO, and CV chondrites are similar to those in chondrules, CAIs, and matrices of their host meteorites and include phyllosilicates, magnetite, carbonates, nepheline, sodalite, grossular, wollastonite, hedenbergite, andradite, and ferrous olivine.Our observations and a thermodynamic analysis suggest that AOAs and forsterite-rich accretionary rims formed in ¹⁶O-rich gaseous reservoirs, probably in the CAI-forming region(s), as aggregates of solar nebular condensates originally composed of forsterite, Fe, Ni-metal, and CAIs. Some of the CAIs were melted prior to aggregation into AOAs and experienced formation of Wark-Lovering rims. Before and possibly after the aggregation, melilite and spinel in CAIs reacted with SiO and Mg of the solar nebula gas enriched in ¹⁶O to form Al-diopside and anorthite. Forsterite in some AOAs reacted with ¹⁶O-enriched SiO gas to form low-Ca pyroxene. Some other AOAs were either reheated in ¹⁶O-poor gaseous reservoirs or coated by ¹⁶O-depleted pyroxene-rich dust and melted to varying degrees, possibly during chondrule formation. The most extensively melted AOAs experienced oxygen isotope exchange with ¹⁶O-poor nebular gas and may have been transformed into magnesian (Type I) chondrules. Secondary mineralization and at least some of the oxygen isotope exchange in AOAs from altered and metamorphosed chondrites must have resulted from alteration in the presence of aqueous solutions after aggregation and lithification of the chondrite parent asteroids.     

Replacement textures in CAI and implications regarding planetary metamorphism

Textural and chemical features of five coarse-grained, calcium-aluminum-rich inclusions from the Allende meteorite indicate that some of the melilite in these inclusions was formed by a secondary metamorphic event and not by primary crystallization from a melt or by a sequential nebular condensation process. These inclusions contain embayed pyroxene surrounded by melilite. Physically separated pyroxene crystals are often in optical continuity indicating that they were once part of larger single crystals that have been partly replaced by melilite. Other evidences of metamorphism include reaction textures between melilite and spinel, and metamorphic textures such as kink-band-like features, lobate sutured grain boundaries, and 120° triple-points. This type of metamorphic process requires the addition of Ca which we propose came from calcite or by introduction of a fluid phase. We believe that the most likely environment for this metamorphic process is on a small planetary body, and not in the solar nebula. The results of this study are compatible with oxygen isotopic heterogeneities within CAI, and provide a mechanism for producing lower temperature alteration phases and the rim phases found in these inclusions. We conclude that planetary processes must thus be considered in the formation history of CAI, and that it is necessary to reconsider the classification system of these objects in light of the replacement process proposed here.     

A comparative study of melilite and fassaite in Types B1 and B2 refractory inclusions

Most of the petrologic data available for Type B inclusions comes from Type B1s. Relatively little comes from the B2s, and there has not been a systematic comparison of the properties of their two most abundant minerals. In this work, we document the compositions and zoning patterns of melilite and fassaite in Type B2 inclusions, and compare and contrast them with the features of their counterparts in Type B1 inclusions. We find that melilite compositions in Type B2 inclusions are similar to those of Type B1s, with maximum Åk contents of ∼75 mol % and a positive correlation between Åk and Na₂O contents. Asymmetrically zoned melilite is common in Type B2s as are melilite grains with reversely zoned regions, and the reversely zoned portions of crystals are thicker than in B1s. In B2s, like B1s, fassaite is zoned with decreasing Ti, Sc, and V oxide contents from cores to rims of grains. Approximately half of the Ti is trivalent, but unlike that in B1s, within fassaite grains in B2s the Ti³⁺/(Ti³⁺ + Ti⁴⁺) ratio does not decrease from core to rim, and sharp enrichments (“spikes”) in Ti³⁺ and V are not observed. Sector-zoned fassaite is much more common in B2s than in B1s. The differences we observed can be accounted for by the differences in bulk compositions between B1s and B2s. Type B2 inclusions tend to have higher SiO₂ contents, hence higher An/Ge component ratios, than Type B1s. Phase equilibria show that, compared to B1s, in B2s less melilite should crystallize prior to the appearance of fassaite, so that in B2s a higher proportion of melilite cocrystallizes with fassaite, causing more of the crystals to be reversely zoned; more melilite crystallizes while adjacent to other crystals, leading to asymmetrical zoning; and with more liquid available, transport of components to growing fassaite occurs more readily than in B1s, facilitating crystal growth and giving rise to sector zoning. The lack of zoning with respect to Ti³⁺/Ti^tot and the absence of Ti³⁺-, V-rich spikes suggest that Type B2 melts maintained equilibrium with the nebular gas throughout crystallization, while the interiors of B1s were probably isolated from the gas, perhaps by their melilite mantles. This makes the similarity of Na-Åk relationships in B1 and B2 melilite difficult to understand, but apparently enclosure by melilite mantles was not necessary for the retention of Na₂O during crystallization of Type B refractory inclusions.