In situ SIMS oxygen isotope analyses: Evidence for the formation of aluminum-rich chondrules from ordinary chondrites

Aluminum-rich chondrules(ARCs),which share mineralogic and chemical properties with both Ca,Al-rich inclusions(CAIs)and ferromagnesian chondrules,play an important role in revealing their temporal and petrogenetic relationships.In this work,seven ARCs were found in three ordinary chondrites GRV 022410(H4),GRV 052722(H3.7)and Julesburg(L3.6).They contain bulk Al2O3~17%-33%and exhibit igneous textures composed of olivine,high-and low-Ca pyroxene,plagioclase,spinel and glass.In situ SIMS analyses show that ARCs have oxygen isotopic compositions(δ18O=–6.1‰–7.1‰;δ17O=–4.5‰–5.1‰)close to ferromagnesian chondrules but far more depleted in 16O than CAIs(δ18O=-40‰;δ17O=-40‰).Most ARCs plot close to the terrestrial mass fractionation(TF)line,and a few between the TF and carbonaceous chondrite anhydrous mixing(CCAM)lines.Plagioclase,nepheline and glass suffered O-isotopic exchanges during the metamorphism processes in the parent body.Spinel,olivine and pyroxene represent the primary O-isotopic compositions of ARCs,and define a fitted line with a slope of~0.7±0.1.Compared with the results of previous studies,shallower slope as well as more depleted16O compositions further demonstrates that ARCs in ordinary chondrites are not a simple mixing product of ferromagnesian chondrules and CAIs.Instead,they probably experienced higher-degree oxygen isotope exchange with a 16O-poor nebular gas reservoir during multiple melting episodes.     

The oxygen isotope record in Murchison and other carbonaceous chondrites

The ranges of δ¹⁸O and δ¹⁷O in components of the Murchison (C2) chondrite exceed those in all other meteorites analyzed. Previous authors have proposed that C2 chondrites are the products of aqueous alteration of anhydrous silicates. A model is presented to determine whether the isotopic variations can be understood in terms of such alteration processes. The minimum number (two) of initial isotopic reservoirs is assumed. Two major stages of reservoir interaction are required: one at high temperature to produce the¹⁶O-mixing line observed for the anhydrous minerals, and another at low temperature to produce the matrix minerals. The isotopic compositions severely constrain the conditions of the low-temperature process, requiring temperatures < 20°C and volume fractions of water > 44%. Extension of the model to the data on C1 chondrites requires aqueous alteration in a warmer, wetter environment.     

Origin of iron-rich olivine in the matrices of type 3 ordinary chondrites: an experimental study

In order to understand the origin of iron-rich olivine in the matrices of type 3 ordinary chondrites, the reaction of metallic iron and enstatite, with and without forsterite and SiO₂, has been experimentally reproduced at temperatures between 1150° and 800°C and P_O2 between 10⁻¹¹ and 10⁻¹⁶ atm (between the IQF and MW buffers). The olivine produced ranges from Fo₅₈ to Fo₃₄ and this composition does not change significantly with temperature and time of the runs. The magnesian olivine which forms does become more magnesian with increasing forsterite/enstatite ratio of the starting materials. Iron-rich olivine (Fo< 35) cannot be formed by the reaction of enstatite and metallic iron, with or without forsterite as starting materials but it can be formed in the presence of free silica. The composition of olivine becomes more iron-rich with increasing silica/enstatite ratio. The compositional range of olivine formed from each mixture is 25–30 mole% Fo regardless of the temperature, composition, mineral assemblage, and run duration.From these experimental results, two possibilities suggested for the origin of the iron-rich olivine in the matrices of type 3 ordinary chondrites: (1) free silica must have been present if the iron-rich olivine was formed by solid-state reactions under oxidizing condition in the solar nebula; (2) reaction of silicon-rich gas with metallic iron took place under oxidizing condition in the solar nebula. Though it is difficult to define which alternative was dominant, the formation of free silica or silicon-rich gas may be a result of fractional condensation. This is possible if there is a reaction relation between forsterite and gas to produce enstatite. The suggested fractional condensation is supported by the fact that the compositions of the fine-grained matrices of type 3 ordinary chondrites are more silica-rich than the bulk compositions of the chondrites. Though it is not known whether such conditions were established all over the nebula or locally in the nebula, both fractionation and more oxidizing conditions than the average solar nebula are required for the formation of matrix olivine.     

Multiple sulfur and oxygen isotope compositions in Beijing aerosol

Multiple sulfur isotopes(32S, 33 S, 34 S, 36S) and oxygen isotopes(16O, 18O) in Beijing aerosols were measured with MAT-253 isotope mass spectrometer. The δ34S values of Beijing aerosol samples range from 1.68‰ to 12.57‰ with an average value of 5.86‰, indicating that the major sulfur source is from direct emission during coal combustion. The δ18O values vary from 5.29‰ to 9.02‰ with an average value of 5.17‰, revealing that the sulfate in Beijing aerosols is mainly composed of the secondary sulfate. The main heterogeneous oxidation of SO2 in atmosphere is related to H2O2 in July and August, whereas H2O2 oxidation and Fe3+ catalytic oxidation with SO2 exist simultaneously in September and October. Remarkable sulfur isotope mass-independent fractionation effect is found in Beijing aerosols, which is commonly attributed to the photochemical oxidation of SO2 in the stratosphere. In addition, thermochemical reactions of sulfur-bearing compounds might be also a source of sulfur isotope anomalies based on the correlation between ?33S and CAPE.     

Ni isotopic compositions in Allende and other meteorites

A new technique for high-precision isotopic analyses of Ni was developed and applied to terrestrial samples, Allende inclusions and materials from other meteorites. Most of the Allende inclusions analysed here were previously reported to contain isotopically anomalous Ti. In contrast, the Ni isotopic abundances are indistinguishable from normal within presently obtainable precision with only one possible exception. The latter inclusion was shown by others to contain a significantly fractionated magnesium isotopic pattern of 9‰/amu. A normal Ni isotopic pattern has also been observed for the chromite/carbon fraction of an Allende acid residue which is known to contain heavy noble gases of highly anomalous isotopic composition. All other meteoritic samples analysed (Khohar matrix and chondrules, Murray matrix, a Tieschitz chondrule and an Orgueil magnetic fraction) also show normal isotopic compositions of Ni; no evidence for effects from now extinct⁶⁰Fe could be detected. In spite of ubiquitous isotopic anomalies in Ti from normal Allende inclusions, there is no signature of isotopic variations in Ni from the same samples. Possible constraints for the nucleosynthesis of iron peak elements and for astrophysical and cosmochemical conditions during formation of the solar system are discussed.     

Exsolution of ilmenite and Cr-Ti magnetite from olivine of garnet-wehrlite

Since coesite-bearing eclogite was found in the Dabie-Sulu area[1-3], the ultrahigh-pressure (UHP) me- tamorphic belt has become a hot topic studying by domestic and overseas scientists. The studying about the forming depth of UHP metamorphic rocks is ex- tremely important, because the peak-metamorphic depth of UHP metamorphic rocks exhumated back to the crust is the key to discuss the processes of magma formation, fluid activity and metamorphism at bottom of orogenic belt. The discovery o…     

Hydrogen and oxygen isotope compositions of eclogites from the Dabie Mountains and geodynamic implications

Heterogeneous δ¹⁸O values as low as - 2.6‰ to+7.0% are observed for ultrahigh pressure eclogites from the Dabie Mountains in East China. Oxygen isotope equilibrium has been approached between the eclogite minerals, suggesting that the rocks would have acquired the unusual δ¹⁸O values prior to ultrahigh pressure metamorphism by interaction with¹⁸O-depleted fluid. δD values of hydroxyl-bearing are between — 51% and - 83‰, precluding the possibility of paleoseawater involvement. The only likely fluid is ancient meteoric water that exchanged oxygen isotopes with the eclogite precursor (a kind of basaltic rocks) formerly resident on the continental crust. This suggests a crustal recycling process in the suture zone of late subduction. Because silicate minerals undergo rapid oxygen isotope exchange at mantle pressures, preservation of the isotopic signature of meteoric water in the eclogites indicates limited crust-mantle interaction and thus a short residence time (<20 Ma) when the plate containing the eclogite precursor was subducted to mantle depths. The agreement in oxygen isotope temperatures for different mineral pairs suggests a rapid cooling and ascent process for the eclogites subsequent to their formation at mantle depths. Project supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences.     

On the origin of isolated olivine grains in type 2 carbonaceous chondrites

The origin of olivine grains isolated in the matrix of C2 carbonaceous chondrites is an important problem. If these grains are condensates from a solar nebular gas, they contain compositional, isotopic and physical features that further elucidate that process. If, however, they are grains released by the breakup of chondrules, then many important condensation features have been lost during the melting that took place to form chondrules.In evaluating these two possibilities, care must be taken to determine which inclusions in C2 meteorites are actual chondrules and which are aggregates of grains that have never undergone melting. The two main types of aggregates, pyroxene-rich and pyroxene-poor, are forty to fifty times more abundant than chondrules. Four scenarios are presented to account for the kinds of aggregates and isolated grains seen in the Murchison C2 meteorite. An analysis of these scenarios is made in light of olivine crystal morphology, comparison of composition of glass inclusions inside olivine grains with interstitial glass in true chondrules and size distributions of olivines, isolated, in aggregates and in chondrules.It is concluded that no scenario that includes a chondrule-making step can account for the observed population of isolated olivine grains. An origin by direct condensation, partial comminution, aggregation and accretion best accounts for the sizes and morphological features observed.     

The compositions of incipient shock melts in L6 chondrites

Microprobe analyses of 33 melt pocket glasses in five L6d and L6e chondrites show them to be chemically varied but typically enriched in the constituents of plagioclase relative to the host meteorites. This enrichment appears to increase with the degree of melting (0–6.5 vol.%), but other chemical variations among the glasses (sodium depletion, reduction of ferrous iron) appear to be unrelated to shock intensity and melt abundance.Chemical trends for melt pocket glasses differ sharply from those reported for chondrules in ordinary chondrites. Thus partial shock melting of chondritic material is an inadequate explanation for the chemical properties of chondrules.     

Microanalysis of nitrogen isotope abundances: association of nitrogen with noble gas carriers in Allende

Current research efforts to explore and account for the distribution of nitrogen isotope abundances in the ancient and present-day solar wind and in meteorites often require measurement of nitrogen abundances and isotopic compositions in very small samples of rare extraterrestrial materials. Isotopic analysis of ～ 1 μg of N₂ is possible with modern techniques of dynamic mass spectrometry, but even this high sensitivity is a limiting factor for certain critical samples. We have utilized a statistically operated mass spectrometer coupled to an ultrahigh vacuum gas extraction and processing system to lower this limit by approximately four orders of magnitude. Quantities of N₂ ranging from ～ 100 ng to < 100 pg are measurable with permil to percent precision in isotope ratios. Nitrogen and all noble gases evolved during stepwise combustion of fine-grained matrix material separated from the Allende meteorite have been meausred simultaneously in a pilot experiment using this technique. Isotopically heavy H-Xe (CCF-Xe) and isotopically light N are co-sited in a carbonaceous carrier phase, supporting a nucleosynthetic origin for¹⁵N-depleted nitrogen in Allende. The great isotopic uniformity of trapped Ar in all carrier phases indicates that simple, physical mass fractionation in gravitational escape of volatiles from the primitive nebula cannot have played a significant role in generating the nitrogen compositions observed in solar system matter.     

Textural evidence bearing on the origin of isolated olivine crystals in C2 carbonaceous chondrites

In some cases the mechanical competence of chondrules in carbonaceous chondrites has been reduced by alteration of their mesostasis glass to friable phyllosilicate, providing a mechanism by which euhedral olivines can be separated from chondrules. Morphological features of isolated olivine grains found in carbonaceous chondrites are similar to those of olivine phenocrysts in chondrules. These observations suggest that the isolated olivine grains formed in chondrules, by crystallization from a liquid, rather than by condensation from a vapor.     

Distribution of lead and thallium in the matrix of the Allende meteorite and the extent of terrestrial lead contamination in chondrites

Selective chemical dissolution has been used to study the distribution of Pb and Tl in an ultrafine ?20-μm matrix separate of Allende. The matrix was exposed to high-purity reagents ranging from H₂O, then HCl of increasing concentration and finally HF-HCl mixtures. A total of 17 extractions were obtained, each for a minimum period of 10 days. The isotopic compositions of the Pb released during the slow dissolution of the matrix fall into four distinct groups. The first, consisting of four extractions, released a component of terrestrial Pb isotopic composition with a total abundance of about 1 ppb. The next six extractions, which contained the bulk of the indigenous Pb and Tl corresponding to 96% and 94%, respectively, of the total matrix abundance, was of a reasonably homogeneous Pb isotopic composition with mean ratios of²⁰⁶Pb²⁰⁴Pb= 10.00and²⁰⁷Pb²⁰⁴Pb= 10.74. In the final seven extractions, the released Pb falls into two higher isotopic groupings and probably results from the dissolution of debris from chondrules and inclusions. The apparent age of the internal matrix isochron is4562 ± 14 My. The release of Pb and Tl shows a reasonable correlation with the matrix dissolution. This indicates that the Pb and Tl reside predominantly within the matrix phases rather than as a localised phase. The Tl isotopic composition of two matrix fractions and whole meteorite were measured and found to be indistinguishable from the terrestrial²⁰⁵Tl/²⁰³Tl ratio. Measurement of a terrestrial reagent standard in the range 1–10 ng Tl gave, for 20 analyses, a mean²⁰⁵Tl/²⁰³Tl ratio of2.38907 ± 0.00102 (2σ).The estimate of terrestrial Pb contamination is considerably lower than the 6–300 ppb assumed in some recent studies in order to explain the phenomenon of apparent excess radiogenic Pb in chondrites. The problem of terrestrial Pb pollution and the evidence which argues against a relatively severe and homogeneous Pb contamination of meteorites, is briefly considered. The apparent initial isotopic composition of the bulk of the indigenous Pb in the Allende matrix was found to be²⁰⁶Pb²⁰⁴Pb= 9.57and²⁰⁷Pb²⁰⁴Pb= 10.47. This is of a higher composition than the Pb in the Can?on Diablo troilite phase and further indicates that the phenomenon of apparent excess radiogenic Pb in chondrites is real.     

Origin of the springtime South China Sea Warm Current in the southwestern Taiwan Strait: Evidence from seawater oxygen isotope

Oxygen isotope(δ~(18)O) of seawater is an excellent proxy for tracing the origins of water masses and their mixing processes. Combining with hydrographic observation, hybrid coordinate ocean model(HYCOM) analysis data, and seawater oxygen isotope, we investigated the source of the South China Sea Warm Current(SCSWC) in the southwestern Taiwan Strait and its underlying mechanism. Results show that the Kuroshio subsurface water(KSSW) can intrude the continental slope in the southwestern Taiwan Strait, and thereby climb up the continental slope coupled with upwelling. The δ~(18)O-salinity relationship further indicates that in spring, the SCSWC in the southwestern Taiwan Strait originates from the upslope deflection of the slope current formed by the KSSW intrusion into the South China Sea, rather than from the west segment of the SCSWC formed to the east of Hainan Island. In addition, the southward flowing Zhe-Min Coastal Current(ZMCC) can reach as far as the Taiwan Bank(TB) and deflects offshore over the western TB at approximately 23.5°N, to some extent affecting the SCSWC. Moreover, this study reveals that seawater δ~(18)O is exquisitely sensitive to the determination of the origin and transport of water masses as compared with traditional potential temperature-salinity plot(θ-S) and HYCOM analysis data. In addition, their coupling can more reliably interpret the mixing processes of shelf water masses.     

Origin of waters responsible for serpentinization of the Izu-Ogasawara-Mariana forearc seamounts in view of hydrogen and oxygen isotope ratios

Many serpentinite seamounts occur over a region 20–120 km west of the trench axis in the Izu-Ogasawara-Mariana forearc regions. The hydrogen and oxygen isotopic compositions of serpentine from these regions indicate that there are at least two kinds of waters responsible for serpentinization: seawater and water derived from dehydration of the descending slab. Serpentine from two Mariana and two Torishima samples with microscopically ductile and sheared texture (sheared-type) have lowerδD(−63to−52‰) and slightly higherδ18O values (+6.1 to +8.2‰) than that of other nine Ogasawara samples with mesh texture (mesh-type) (δD= −43to−49‰ andδ¹⁸O= +5.8to+6.7‰). This suggests that the sheared-type serpentine with lowerδD and slightly higherδ¹⁸O values was formed within the wedge mantle by interaction with water derived from a descending slab. The sheared texture is likely to have been produced during diapiric uplift. The unaltered portion of the ultramafic bodies later interacted with seawater after emplacement at or near the seafloor, resulting in formation of the mesh-type serpentine with higherδD values.     

The Niger (I) carbonaceous chondrite and implications for the origin of aggregates and isolated olivine grains in C2 chondrites

The origin of olivine grains in C2 carbonaceous chondrites is a controversial topic: directly condensed material or detrital remnants of preexisting chondrules? This study shows that the Niger C2 meteorite is similar to Murchison but reveals several interesting features in relation to the origin of the olivine. Microprobe analysis of olivine (Si, Fe, Mg, Ca, Mn, Cr), glass and nickel-iron inclusions within the grains, and Fe-S-O phase as well as the relationships between the olivine grains in the aggregates, between the grains and the interstitial phyllosilicate matrix, between the inclusions and their host olivine grains, and the morphology of some aggregates all show that two populations of olivine coexist, probably crystallized from chondrule melts rather than by direct condensation from a solar nebula gas. The characteristics of the nickel-iron inclusions within the olivine suggest a magmatic chondrule-making stage from previously condensed materials.     

Calculation of oxygen isotope fractionation in hydroxyl-bearing silicates

The modified increment method has been applied to the calculation of oxygen isotope fractionation factors for hydroxyl-bearing silicate minerals. The order of ¹⁸O enrichment obtained in common rock-forming minerals is: pyrophyllite > kaolinite > tourmaline talc > prehnite topaz > illite > phengite > lepidolite muscovite staurolite > epidote > glaucophane > serpentine chlorite > tremolite > hornblende > phlogopite biotite > humite > norbergite > ilvaite. Hydroxyl-bearing silicates are enriched in ¹⁸O relative to hydroxyl groups but depleted in ¹⁸O relative to anhydrous counterparts.

Three sets of self-consistent fractionation factors: between quartz and the hydroxyl-bearing silicate minerals, between calcite and the silicate minerals, and between the silicate minerals and water, have been calculated for a temperature range of 0–1200°C. The fractionation factors calculated for mineral pairs are applicable to isotopic geothermometry in igneous, metamorphic and sedimentary petrology. They can be used as a test of isotopic equilibrium or disequilibrium in natural mineral assemblages over all temperature ranges of geological interest. The difference in oxygen isotope composition between the hydroxyl-bearing mineral and the OH group is quantitatively demonstrated to be temperature dependent and, therefore, can be used as a single-mineral geothermometer.     

Lithium isotope composition of ordinary and carbonaceous chondrites, and differentiated planetary bodies: Bulk solar system and solar reservoirs

In order to better constrain the Li isotope composition of the bulk solar system and Li isotope fractionation during accretion and parent body processes, Li isotope compositions and concentrations were determined on a number of meteorite falls and finds. This is the first comprehensive study that systematically investigates a representative set of samples from carbonaceous chondrites (CI, CM2, CO3, CV3, CK4 and one ungrouped member), enstatite chondrites (EH, EL), ordinary chondrites (H, L, LL), and achondrites (one eucrite, diogenites, one pallasite, and a silicate inclusion from a IAB iron).

Carbonaceous chondrites have an average isotope composition of δ⁷Li = + 3.2‰ ± 1.9 (2σ) which agrees with the average composition of relatively pristine olivines (representative for the bulk composition) from the Earth primitive upper mantle (PUM). This is lighter than the average δ⁷Li of the basaltic differentiates of the Earth, Moon and Mars and the achondrites. It is an important observation, however, that the lighter end of the isotopic range of the differentiates always coincides with the averages of the mantle olivines and the carbonaceous chondrites. From this we conclude that the bulk of the inner solar system consists mostly of material from carbonaceous chondrites and that the variation seen in the differentiates is due to planetary body processes. Ordinary chondrites are significantly lighter than carbonaceous chondrites. No significant differences in δ⁷Li exist between enstatite chondrites (n = 3) and carbonaceous or ordinary chondrites. The difference between carbonaceous and ordinary chondrites and the variability within the chondrites could indicate the existence of distinct Li isotope reservoirs in the early solar nebula.     

Effect of enstatite activity and oxygen partial pressure on the point-defect chemistry of olivine

The variation of the point-defect concentrations in olivine with changes in enstatite activity and oxygen partial pressure are derived from formal thermodynamic arguments. Two models for these variations are constructed; the models differ in the choice of the approximate charge-neutrality condition in the near-stoichiometric regime. Under favorable circumstances, the effect of the oxygen partial pressure on olivine's point-defect chemistry can provide a diagnostic technique. Activity differences within the upper mantle may have a significant effect on olivine's transport properties because of their effect on the point-defect concentrations. The activity of enstatite plays an important role in the point-defect chemistry of olivine.