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1.
Mass-independent isotope effects in Archean (2.5 to 3.8 Ga) sedimentary sulfides determined by ion microprobe analysis 总被引：1，自引：0，他引：1
We report sulfur isotope anomalies with Δ33S, the deviation from a mass-dependent fractionation line for the three-isotope system (34S/32S vs. 33S/32S), ranging up to ±2‰ within individual Archean sedimentary sulfides from a variety of localities. Our measurements, which are made in situ by multicollector secondary ion mass spectrometry, unequivocally corroborate prior bulk measurements of mass-independent fractionations (MIF) in sulfur and provide additional evidence for an anoxic atmosphere on the Earth before ∼2 Ga. This technique also offers new opportunities for exploring ancient sulfur metabolisms preserved in the rock record. The presence of MIF sulfur in sulfides from a >3.8-Ga Fe-rich quartzite from Akilia (island), West Greenland, is consistent with a marine sedimentary origin for this rock. 相似文献
2.
Cécile Engrand Kevin D. McKeegan Gregory F. Herzog Laurence E. Nyquist 《Geochimica et cosmochimica acta》2005,69(22):5365-5385
Large, correlated, mass-dependent enrichments in the heavier isotopes of O, Cr, Fe, and Ni are observed in type-I (metal/metal oxide) cosmic spherules collected from the deep sea. Limited intraparticle variability of oxygen isotope abundances, typically <5‰ in δ18O, indicates good mixing of the melts and supports the application of the Rayleigh equation for the calculation of fractional evaporative losses during atmospheric entry. Fractional losses for oxygen evaporation from wüstite, assuming a starting isotopic composition equal to that of air (δ18O = 23.5‰; δ17O = 11.8‰), are in the range 55%-77%, and are systematically smaller than evaporative losses calculated for Fe (69%-85%), Cr (81%-95%), and especially Ni (45%-99%). However, as δ18O values increase, fractional losses for oxygen approach those of Fe, Cr, and Ni indicating a shift in the evaporating species from metallic to oxidized forms as the spherules are progressively oxidized during entry heating. The observed unequal fractional losses of O and Fe can be reconciled by allowing for a kinetic isotope mass-dependent fractionation of atmospheric oxygen during the oxidation process and/or that some metallic Fe may have undergone Rayleigh evaporation before oxidation began.In situ measurements of oxygen isotopic abundances were also performed in 14 type-S (silicate) cosmic spherules, 13 from the Antarctic ice and one from the deep sea. Additional bulk Fe and Cr isotopic abundances were determined for two type-S deep-sea spherules. The isotopic fractionation of Cr isotopes suggest appreciable evaporative loss of Cr, perhaps as a sulfide. The oxygen isotopic compositions for the type-S spherules range from δ18O = −2‰ to + 27‰. The intraspherule isotopic variations are typically small, ∼5% relative, except for the less-heated porphyritic spherules which have preserved large isotopic heterogeneities in at least one case. A plot of δ17O vs. δ18O values for these spherules defines a broad parallelogram bounded at higher values of δ17O by the terrestrial fractionation line, and at lower values of δ17O by a line parallel to it and anchored near the isotopic composition of δ18O = −2.5‰ and δ17O = −5‰. Lack of independent evidence for substantial evaporative losses suggests that much of this variation reflects the starting isotopic composition of the precursor materials, which likely resembled CO, CM, or CI chondrites. However, the enrichments in heavy isotopes indicate that some mixing with atmospheric oxygen was probably involved during atmospheric entry for some of the spherules. Isotopic fractionation due to evaporation of incoming grain is not required to explain most of the oxygen isotopic data for type-S spherules. However spherules with barred olivine textures that are thought to have experienced a more intense heating than the porphyritic ones might have undergone some distillation. Two cosmic spherules, one classified as a radial pyroxene type and the other showing a glassy texture, show unfractionated oxygen isotopic abundances. They are probably chondrule fragments that survived atmospheric entry unmelted.Possible reasons type-I spherules show larger degrees of isotopic fractionation than type-S spherules include: a) the short duration of the heating pulse associated with the high volatile content of the type-S spherule precursors compared to type-I spherules; b) higher evaporation temperatures for at least a refractory portion of the silicates compared to that of iron metal or oxide; c) lower duration of heating of type-S spherules compared to type-I spherules as a consequence of their lower densities. 相似文献
3.
Carolyn A. Crow Desmond E. Moser Kevin D. McKeegan 《Meteoritics & planetary science》2019,54(1):181-201
During impact events, zircons develop a wide range of shock metamorphic features that depend on the pressure and temperature conditions experienced by the zircon. These conditions vary with original distance from impact center and whether the zircon grains are incorporated into ejecta or remain within the target crust. We have employed the range of shock metamorphic features preserved in >4 Ga lunar zircons separated from Apollo 14 and 15 breccias and soils in order to gain insights into the impact shock histories of these areas of the Moon. We report microstructural characteristics of 31 zircons analyzed using electron beam methods including electron backscatter pattern (EBSP) and diffraction (EBSD). The major results of this survey are as follows. (1) The abundance of curviplanar features hosting secondary impact melt inclusions suggests that most of the zircons have experienced shock pressures between 3 and 20 GPa; (2) the scarcity of recrystallization or decomposition textures and the absence of the high‐pressure polymorph, reidite, suggests that few grains have been shocked to over 40 GPa or heated above 1000 °C in ejecta settings; (3) one grain exhibits narrow, arc‐shaped bands of twinned zircon, which map out as spherical shells, and represent a novel shock microstructure. Overall, most of the Apollo 14 and 15 zircons exhibit shock features similar to those of terrestrial zircon grains originating from continental crust below large (~200 km) impact craters (e.g., Vredefort impact basin), suggesting derivation from central uplifts or uplifted rims of large basins or craters on the Moon and not high‐temperature and ‐pressure ejecta deposits. 相似文献
4.
Magnetite in the oxidized CV chondrite Allende mainly occurs as spherical nodules in porphyritic-olivine (PO) chondrules, where it is associated with Ni-rich metal and/or sulfides. To help constrain the origin of the magnetite, we measured oxygen isotopic compositions of magnetite and coexisting olivine grains in PO chondrules of Allende by an in situ ion microprobe technique. Five magnetite nodules form a relatively tight cluster in oxygen isotopic composition with delta 18O values from -4.8 to -7.1% and delta 17O values from -2.9 to -6.3%. Seven coexisting olivine grains have oxygen isotopic compositions from -0.9 to -6.3% in delta 18O and from -4.6 to -7.9% in delta 17O. The delta 17O values of the magnetite and coexisting olivine do not overlap; they range from -0.4 to -2.6%, and from -4.0 to -5.7%, respectively. Thus, the magnetite is not in isotopic equilibrium with the olivine in PO chondrules, implying that it formed after the chondrule formation. The delta 17O of the magnetite is somewhat more negative than estimates for the ambient solar nebula gas. We infer that the magnetite formed on the parent asteroid by oxidation of metal by H2O which had previously experienced minor O isotope exchange with fine-grained silicates. 相似文献
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Multiple sulfur isotopes of sulfides from sediments in the aftermath of Paleoproterozoic glaciations
D. Papineau S.J. Mojzsis C.D. Coath K.D. McKeegan 《Geochimica et cosmochimica acta》2005,69(21):5033-5060
Geochemical evidence reported from Paleoproterozoic sediments has long been used to evaluate the transition from the anoxic Archean atmosphere to an oxygenated atmosphere. Sulfur isotopes (32S, 33S, 34S and 36S) in sedimentary sulfides and sulfates are an especially sensitive means to monitor this transition, such that the timing of the Paleoproterozoic “Great Oxidation Event” can be investigated using mass-independently fractionated (MIF) sulfur isotope systematics expressed as Δ33S. Here we report data from 83 individual analyses of pyrite, pyrrhotite and chalcopyrite on a new suite of 30 different samples from Finland, South Africa, Wyoming and Ontario that span ∼600 My and follow one or several “Snowball Earth” events in the Paleoproterozoic. The samples were measured using a high-resolution secondary ion mass spectrometry technique in multicollection mode that investigates multiple sulfur isotopes in microdomains (<30 μm) within individual sulfide grains while preserving petrographic context. We focused on sediments deposited in the aftermath of the Paleoproterozoic glaciations (between 1.9 and 2.2 Ga) to trace fluctuations in atmospheric O2 concentrations that were likely affected by an interplay of O2 sinks in the atmosphere and the upper ocean and continental crust, and by the emergence and diversification of aerobic organisms. Our results demonstrate that MIF sulfur isotopes are absent in sediments deposited after the period of protracted global cooling in the Paleoproterozoic and independently confirm observations that MIF ceased during this time. We interpret our results by integrating Δ33S and δ34S data in sulfides, δ13C data in carbonates and the estimated timing of glaciation events in the Paleoproterozoic. Data strongly hint at the presence of microbial sulfate reduction and fluctuations in the concentration of dissolved seawater sulfate and/or in δ34Ssulfate in the aftermath of glaciations and likely were affected by changing erosion rates and nutrient delivery to the oceans. These changes modulated the population of primary producers, especially oxygenic photosynthesizers, and led to fluctuations in the abundance of atmospheric O2, CO2 and CH4. Our results support the interpretation that the world-wide δ13Ccarb excursion observed between ∼2.25 and 2.05 Ga (Karhu and Holland, 1996) was a period of significant accumulation of O2 in the atmosphere. 相似文献
7.
E. T. Dunham A. Sheikh D. Opara N. Matsuda M.-C. Liu K. D. McKeegan 《Meteoritics & planetary science》2023,58(5):643-671
As the Sun was forming, calcium–aluminum-rich inclusions (CAIs) were the first rocks to have condensed in the hottest regions of the solar nebula disk. Carbonaceous chondrites (CCs) contain abundant CAIs but are thought to have accreted in the outer Solar System, requiring that CAIs must have been transported outward. Curiously, CAIs are rare in ordinary, enstatite, rumuruti, and kakangari chondrites, non-carbonaceous chondrites (NCs), that likely formed in the inner Solar System. Thus, CAI abundances and characteristics can provide constraints on the early dynamical evolution of the disk. In this work, we address whether the hypothesis of an early-formed proto-Jupiter “opening a gap” in the disk can explain the dichotomy in the relative abundance of CAIs in CC and NC chondrites. We searched 76 NC meteorite sections to find 232 CAIs which have an average apparent diameter of 46 μm and comprise 0.01 area%, about half the size of and ~200 times less abundant than CC CAIs on average. Unlike CC CAIs, only 4% of the NC CAIs contain melilite and most contain alteration features suggesting that NC CAIs underwent pervasive fluid-assisted thermal metamorphism on asteroidal parent bodies. However, based on NC CAI populations correlating with meteorite metamorphic grade, we argue that disk dynamics is likely the primary reason behind the existence of small (<100 μm) and rare NC CAIs. Our data support astrophysical models which suggest that, after outward transport of CAIs, formation of a gap in the disk trapped CAIs in the outer Solar System. 相似文献
8.
Yunbin Guan Gary R. Huss Laurie A. Leshin Glenn J. MacPherson Kevin D. McKeegan 《Meteoritics & planetary science》2006,41(1):33-47
Abstract— Correlated in situ analyses of the oxygen and magnesium isotopic compositions of aluminum‐rich chondrules from unequilibrated enstatite chondrites were obtained using an ion microprobe. Among eleven aluminum‐rich chondrules and two plagioclase fragments measured for 26Al‐26Mg systematics, only one aluminum‐rich chondrule contains excess 26Mg from the in situ decay of 26Al; the inferred initial ratio (26Al/27Al)o = (6.8 ± 2.4) × 10?6 is consistent with ratios observed in chondrules from carbonaceous chondrites and unequilibrated ordinary chondrites. The oxygen isotopic compositions of five aluminum‐rich chondrules and one plagioclase fragment define a line of slope ?0.6 ± 0.1 on a three‐oxygen‐isotope diagram, overlapping the field defined by ferromagnesian chondrules in enstatite chondrites but extending to more 16O‐rich compositions with a range in δ18O of about ?12‰. Based on their oxygen isotopic compositions, aluminum‐rich chondrules in unequilibrated enstatite chondrites are probably genetically related to ferromagnesian chondrules and are not simple mixtures of materials from ferromagnesian chondrules and calcium‐aluminum‐rich inclusions (CAIs). Relative to their counterparts from unequilibrated ordinary chondrites, aluminum‐rich chondrules from unequilibrated enstatite chondrites show a narrower oxygen isotopic range and much less resolvable excess 26Mg from the in situ decay of 26Al, probably resulting from higher degrees of equilibration and isotopic exchange during post‐crystallization metamorphism. However, the presence of 26Al‐bearing chondrules within the primitive ordinary, carbonaceous, and now enstatite chondrites suggests that 26Al was at least approximately homogeneously distributed across the chondrite‐forming region. 相似文献
9.
Calcium‐aluminum‐rich inclusions and amoeboid olivine aggregates from the CR carbonaceous chondrites
Jrme Alon Alexander N. Krot Kevin D. McKeegan 《Meteoritics & planetary science》2002,37(12):1729-1755
Abstract— Calcium‐aluminum‐rich refractory inclusions (CAIs) in CR chondrites are rare (<1 vol%), fairly small (<500 μm) and irregularly‐shaped, and most of them are fragmented. Based on the mineralogy and petrography, they can be divided into grossite ± hibonite‐rich, melilite‐rich, and pyroxene‐anorthite‐rich CAIs. Other types of refractory objects include fine‐grained spinel‐melilite‐pyroxene aggregates and amoeboid olivine aggregates (AOAs). Some of the pyroxene‐anorthite‐rich CAIs have igneous textures, and most melilite‐rich CAIs share similarities to both the fluffy and compact type A CAIs found in CV chondrites. One major difference between these CAIs and those in CV, CM, and CO chondrites is that secondary mineral phases are rare. In situ ion microprobe analyses of oxygen‐isotopic compositions of 27 CAIs and AOAs from seven CR chondrites demonstrate that most of the CAIs are 16O‐rich (δ17O of hibonite, melilite, spinel, pyroxene, and anorthite < ?22‰) and isotopically homogeneous within 3–4‰. Likewise, forsterite, spinel, anorthite, and pyroxene in AOAs have nearly identical, 16O‐rich compositions (?24‰ < δ17O < ?20‰). In contrast, objects which show petrographic evidence for extensive melting are not as 16O‐rich (δ17O less than ?18‰). Secondary alteration minerals replacing 16O‐rich melilite in melilite‐rich CAIs plot along the terrestrial fractionation line. Most CR CAIs and AOAs are mineralogically pristine objects that largely escaped thermal metamorphism and secondary alteration processes, which is reflected in their relatively homogeneous 16O‐rich compositions. It is likely that these objects (or their precursors) condensed in an 16O‐rich gaseous reservoir in the solar nebula. In contrast, several igneous CAIs are not very enriched in 16O, probably as a result of their having melted in the presence of a relatively 16O‐poor nebular gas. If the precursors of these CAIs were as 16O‐rich as other CR CAIs, this implies either temporal excursions in the isotopic composition of the gas in the CAI‐forming regions and/or radial transport of some CAI precursors into an 16O‐poor gas. The absence of oxygen isotope heterogeneity in the primary minerals of melilite‐rich CAIs containing alteration products suggests that mineralogical alteration in CR chondrites did not affect oxygen‐isotopic compositions of their CAIs. 相似文献
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