Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

Mineralogical characterization of a unique material having heavy oxygen isotope anomaly in matrix of the primitive carbonaceous chondrite Acfer 094

We report the mineral compositions and micro-texture of the isotopically anomalous (δ^17,18O_SMOW ∼ +180‰) Fe-S-Ni-O material recently discovered in matrix of the primitive carbonaceous chondrite Acfer 094 [Sakamoto N., Seto Y., Itoh S., Kuramoto K., Fujino K., Nagashima K., Krot A. N. and Yurimoto H. (2007) Oxygen isotope evidence for remnants of the early solar system primordial water. Science317, 231-233]. Synchrotron radiation X-ray diffraction and transmission electron microscopy studies indicate that this material consists of the symplectitically intergrown magnetite (Fe₃O₄) and pentlandite (Fe_5.7Ni_3.3S₈) with magnetite/pentlandite volume ratio of ∼2.3. Magnetite forms column-shaped grains (10-30 nm in diameter and 100-200 nm in length); pentlandite occurs as worm-shaped grains or aggregates of grains 100-300 nm in size between magnetite crystals. Although both the X-ray diffraction and electron energy loss spectra support identification of iron oxide as magnetite, the electron diffraction patterns show that magnetite has a weak 3-fold superstructure, possibly due to ordering of vacancies. We infer that the isotopically anomalous symplectite formed by sulfurization and oxidization of metal grains either in the solar nebula or on an icy planetesimal. The intersite cation distribution of pentlandite suggests that timescale of oxidation was no longer than 1000 years.     

Patterns in the hydrogen and trace element compositions of mantle olivines

 The concentrations of hydrogen and the other trace elements in olivines from mantle xenoliths have been determined by secondary ion mass spectrometry (SIMS) for clarifying the incorporation mechanism and the behavior of the hydrogen. The hydrogen contents in olivines from mantle xenoliths range from 10 to 60 ppm wt. H₂O and the concentration range is consistent with the previous infrared (IR) spectroscopic data. IR spectra of the olivine crystals show no effects of the weathering or secondary alteration. The hydrogen is distributed homogeneously among olivine grains in each mantle xenolith. However, the hydrogen contents of the olivine crystals are less than those for the olivine phenocrysts crystallized from the host magma. Olivine inclusions in diamonds also show similar hydrogen contents to the xenolithic olivines. Thus the hydrogen content of xenolithic olivines does not attain equilibrium with water in the host magma during the transportation from the Earth's mantle to the surface, and is taken as a reflection of the hydrogen condition in the mantle. Correlations of hydrogen with trivalent cation contents in garnet peridotitic olivines indicate the incorporation of hydrogen into mantle olivines by a coupled substitution mechanism, with the hydrogen present in the form of hydroxyl in oxygen positions adjacent to the M site vacancies. The hydrogen content of xenolithic olivines increases with pressure but decreases with increasing temperature, suggesting importance of olivine as a water reservoir at low temperature regions such as in subducting slabs. Received August 15, 1995/Revised, accepted November 19, 1996     

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.     

Co2+ and Ni2+ diffusion in olivine determined by secondary ion mass spectrometry

Diffusion coefficients of Co²⁺ and Ni²⁺ in synthetic single crystal forsterite along the c-axis were determined in the temperature ranges, 700–1200?°C and 800–1300?°C, respectively. The synthesized forsterite specimens were coated with thin evaporated films of CoO and NiO on the c-surface and annealed for diffusion experiments. The short penetration distance of diffusing ions in forsterite was measured by secondary ion mass spectrometry using the depth profile method. The diffusion coefficients of Co (700–1200?°C) and Ni (800–1300?°C) are given by: and The observed diffusion coefficient values show good linear relationships in Arrhenius plots and the activation energy values obtained agree well with the previous values, although the diffusion coefficient values observed at the high temperature end of the experimental range deviate from the previous values. These results indicate that Co and Ni diffuse in olivine with a single mechanism within the temperature range observed, possibly with an extrinsic in nature as in the case of Mg tracer diffusion observed by Chakraborty et?al. 1994 and of Fe-Mg interdiffusion by Chakraborty.     

Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts

Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998     

A study of Mg and K isotopes in Allende CAIs: Implications to the time scale for the multiple heating processes

Abstract— The measurements of magnesium and potassium isotopic compositions of refractory minerals in Allende calcium‐aluminum‐rich inclusions (CAIs), 7R‐19–1, HN3–1, and EGG3 were taken by secondary ion mass spectrometry (SIMS). The 7R‐19–1 contains ¹⁶O‐rich and ¹⁶O‐poor melilite grains and define a single isochron corresponding to an initial ²⁶Al/²⁷Al ratio of (6.6 ± 1.3) × 10^?5. The Al‐Mg isochron, O isotope measurements and petrography of melilite in 7R‐19–1 indicate that ¹⁶O‐poor melilite crystallized within 0.4 Myr after crystallization of ¹⁶O‐rich melilite, suggesting that oxygen isotopic composition of the CAI‐forming region changed from ¹⁶O‐rich to ¹⁶O‐poor within this time interval. The ¹⁶O‐poor melilite is highly depleted in K compared to the adjacent ¹⁶O‐rich melilite, indicating evaporation during remelting of 7R‐19–1. We determined the isochron for ⁴¹Ca‐⁴¹K isotopic systematics in EGG3 pyroxene with (4.1 ± 2.0) × 10^?9 (2s?) as an initial ratio of ⁴¹Ca/⁴⁰Ca, which is at least two times smaller than the previous result (Sahijipal et al. 2000). The ratio of ⁴¹Ca/⁴⁰Ca in the EGG3 pyroxene grain agrees within error with the value obtained by Hutcheon et al. (1984). No evidence for the presence of ⁴¹K excess (decay product of a short‐lived radionuclide ⁴¹Ca) was found in 7R‐19–1 and HN3–1. We infer that the CAI had at least an order of magnitude lower than canonical ⁴¹Ca/⁴⁰Ca ratio at the time of the CAI formation.     

Emplacement mechanisms of the South Kona slide complex,Hawaii Island: sampling and observations by remotely operated vehicle Kaiko

Emplacement of a giant submarine slide complex, offshore of South Kona, Hawaii Island, was investigated in 2001 by visual observation and in-situ sampling on the bench scarp and a megablock, during two dives utilizing the Remotely Operated Vehicle (ROV) Kaiko and its mother ship R/V Kairei. Topography of the bench scarp and megablocks were defined in 3-D perspective, using high-resolution digital bathymetric data acquired during the cruise. Compositions of 34 rock samples provide constraints on the landslide source regions and emplacement mechanisms. The bench scarp consists mainly of highly fractured, vesiculated, and oxidized aa lavas that slumped from the subaerial flank of ancestral Mauna Loa. The megablock contains three units: block facies, matrix facies, and draped sediment. The block facies contains hyaloclastite interbedded with massive lava, which slid from the shallow submarine flank of ancestral Mauna Loa, as indicated by glassy groundmass of the hyaloclastite, low oxidation state, and low sulfur content. The matrix facies, which directly overlies the block facies and is similar to a lahar deposit, is thought to have been deposited from the water column immediately after the South Kona slide event. The draped sediment is a thin high-density turbidite layer that may be a distal facies of the Alika-2 debris-avalanche deposit; its composition overlaps with rocks from subaerial Mauna Loa. The deposits generated by the South Kona slide vary from debris avalanche deposit to turbidite. Spatial distribution of the deposits is consistent with deposits related to large landslides adjacent to other Hawaiian volcanoes and the Canary Islands.     

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.