Structural, chemical, and isotopic microanalytical investigations of graphite from supernovae     

T.Kevin Croat  Thomas Bernatowicz  Scott Messenger 《Geochimica et cosmochimica acta》2003,67(24):4705-4725

We report the results of coordinated ion microprobe and transmission electron microscope (TEM) studies of presolar graphites from the KE3 separate (1.65-1.72 g/cm³) of the Murchison CM2 meteorite. Isotopic analysis of individual graphites (1-12 μm) with the ion microprobe shows many to have large ¹⁸O excesses combined with large silicon isotopic anomalies, indicative of a supernova (SN) origin. Transmission electron microscopy (TEM) of ultramicrotome slices of these SN graphites revealed a high abundance (25-2400 ppm) of internal titanium carbides (TiCs), with a single graphite in some cases containing hundreds of TiCs. Isotopic compositions of individual TiCs by nanoscale resolution secondary ion mass spectrometry (NanoSIMS) confirmed their presolar origin. In addition to TiCs, composite TiC/Fe grains (TiCs with attached iron-nickel subgrains) and solitary kamacite internal grains were found. In the composite grains, the attached iron phase (kamacite [0-24 at. % Ni] or taenite [up to 60 at. % Ni]) was epitaxially grown onto one or more TiC faces. In contrast to the denser Murchison KFC1 graphites, no Zr-Ti-Mo carbides were observed. The average TiC diameters were quite variable among the SN graphites, from 30 to 232 nm, and were generally independent of the host graphite size. TiC grain morphologies ranged from euhedral to anhedral, with the grain surfaces exhibiting variable degrees of corrosion, and sometimes partially amorphous rims (3 to 15 nm thick). Partially amorphous rims of similar thickness were also observed on some solitary kamacite grains. We speculate that the rims on the internal grains are most plausibly the result of atom bombardment caused by drift of grains with respect to the ambient gas, requiring relative outflow speeds ∼100 km/s (i.e., a few percent of the SN mass outflow speed).Energy dispersive X-ray spectrometry (EDXS) of TiCs revealed significant V in solid solution, with an average V/Ti ratio over all TiCs of ∼83% of the solar value of 0.122. Significant variations about the mean V/Ti ratio were also seen among TiCs in the same graphite, likely indicating chemical equilibration with the surrounding gas over a range of temperatures. In general, the diversity in internal TiC properties suggests that TiCs formed first and had substantially diverse histories before incorporation into the graphite, implying some degree of turbulent mixing in the SN outflows.In most graphites, there is a decrease in the number density of TiCs as a function of increasing radial dis- tance, caused by either preferential depletion of TiCs from the gas or an acceleration of graphite growth with decreasing ambient temperature. In several graphites, TiCs showed a trend of larger V/Ti ratios with increasing distance from the graphite center, an indication of progressive equilibration with the surrounding gas before they were sequestered in the graphites. In all but one graphite, no trend was seen in the TiC size vs. distance from the graphite center, implying that appreciable TiC growth had effectively stopped before the graphites formed, or else that graphite growth was rapid compared to TiC growth. Taken together, the chemical variations among internal grains as well as the presence of partially amorphous rims and epitaxial Fe phases on some TiCs clearly indicate that the phase condensation sequence was TiC, followed by the iron phases (only found in some graphites) and finally graphite. Since graphite typically condenses at a higher temperature than iron at low pressures (<10⁻³ bars) in a gas with C > O and otherwise solar composition, the observed condensation sequence implies a relative iron enrichment in the gas or greater supersaturation of graphite relative to iron.The TEM observations allow inferences to be made about the physical conditions in the gas from which the grains condensed. Given the TiC sizes and abundances, the gas was evidently quite dusty. From the observed TiC size range of ∼20 nm to ∼500 nm (assuming ∼1 yr growth time and T ∼ 1800°K), we infer minimum Ti number densities in the gas to be ∼7 × 10⁴ to ∼2 × 10⁶ atoms/cc, respectively. Although the gas composition is clearly not solar, for scale, these number densities would correspond to a pressure range of ∼0.2 μbar to ∼5.0 μbar in a gas of solar composition. They also correspond to minimum TiC grain number densities of ∼3 × 10⁻⁴ to ∼0.2 grains/cc, assuming complete condensation of Ti in TiC. We estimate the maximum ratio of mean TiC grain separation distance in the gas to grain diameter from the Ti number densities as ∼3 × 10⁵ to ∼1 × 10⁶.  相似文献   

Comments on Wyatt & Cave's ‘The Chalfield Oolite Formation (Bathonian, Middle Jurassic) and the Forest Marble overstep in the South Cotswolds and the stratigraphical position of the Fairford Coral Bed’ and reply by the authors: Proceedings, Vol. 113, 2002, pp. 139-152     

Michael G. Sumbler 《Proceedings of the Geologists' Association. Geologists' Association》2003,114(2):181-191

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Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite     

E. J. Palin  M. T. Dove  S. A. T. Redfern  C. I. Saniz-Díaz  W. T. Lee 《Physics and Chemistry of Minerals》2003,30(5):293-304

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.  相似文献   

Spectral and Multiscale Signal-to-Noise Thresholding of Spherical Vector Fields   总被引：1，自引：0，他引：1  

W. Freeden  T. Maier 《Computational Geosciences》2003,7(3):215-250

The basic concepts of spectral and multiscale selective reconstruction of (geophysically relevant) vector fields on the sphere from error-affected data is outlined in detail. The reconstruction mechanism is formulated under the assumption that spectral as well as multiscale approximation is well-representable in terms of only a certain number of expansion coefficients at the various resolution levels. It is shown that spectral denoising by means of orthogonal expansions in terms of vector spherical harmonics reflects global a priori information of the noise (e.g., in form of a covariance tensor field), whereas multiscale signal-to-noise thresholding can be performed under locally dependent noise information within a multiresolution analysis in terms of spherical vector wavelets. An application of the multiscale formalism to Earth's magnetic field determination is presented.  相似文献   

Source of trace element variability in Great Barrier Reef corals affected by the Burdekin flood plumes     

Chantal Alibert  Les Kinsley  Malcolm T. McCulloch  Felicity McAllister 《Geochimica et cosmochimica acta》2003,67(2):231-246

Massive corals in the Great Barrier Reef, analyzed at high-resolution for Sr/Ca (thermal ionization mass spectrometry) and trace elements such as Ba and Mn (laser ablation inductively coupled plasma mass spectrometry), can provide continuous proxy records of dissolved seawater concentrations, as well as sea surface temperature (SST). A 10-yr record (1989 to 1998) from Pandora Reef, an inshore reef regularly impacted by the freshwater plumes of the Burdekin River, is compared with an overlapping record from a midshelf reef, away from runoff influences. Surface seawater samples, taken away from river plumes, show little variability for Sr/Ca (8484 ± 10 μmol/mol) and Ba (33.7 ± 0.7 nmol/kg). Discrete Ba/Ca peaks in the inshore coral coincide with flood events. The magnitude of this Ba/Ca enrichment is most likely controlled by the amount of suspended sediments delivered to the estuary, which remains difficult to monitor. The maximum flow rate at peak river discharge is used here as a proxy for the sediment load and is shown to be strongly correlated with coral Ba/Ca (r = 0.97). After the wet summer of 1991, the coral Ba/Ca flood peak is followed by a plateau that lingers for several months after dissipation of plume waters, signifying an additional flux of Ba that may originate from submarine groundwater seeps and/or mangrove reservoirs. Both Mn and Y are enriched by a factor of ∼5 in inshore relative to midshelf corals. Mn/Ca ratios show a seasonal cycle that follows SST (r = 0.7), not river discharge, with an additional high variability in summer suggesting a link with biological activity. P and Cd show no significant seasonal variation and are at a low level at both inshore and midreef locations. However, leaching experiments suggest that part of the coral P is not lattice bound.  相似文献   

Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C     

A. Stefánsson  T.M. Seward 《Geochimica et cosmochimica acta》2003,67(7):1395-1413

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.  相似文献   

Citation for presentation of the Distinguished Service Award to Denis M. Shaw     

Michael J. Drake 《Geochimica et cosmochimica acta》2003,67(13):2317-2318

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Oxygen isotope systematics in Diploastrea heliopora: new coral archive of tropical paleoclimate     

Tsuyoshi Watanabe  Michael K. Gagan  Heather Scott-Gagan  Wahyoe S. Hantoro 《Geochimica et cosmochimica acta》2003,67(7):1349-1358

Diploastrea heliopora forms dense, robust, dome-shaped coral colonies throughout the reef ecosystems of the tropical Pacific and Indian Oceans. This slow-growing (2 to 6 mm/yr) coral has the potential to yield continuous paleoclimate records spanning up to 1000 yr for the warmest waters on Earth, the Indo-Pacific Warm Pool, and has a long fossil history as a single recognizable species. Despite the potential of Diploastrea to be an important new paleoclimate archive, little is known about the systematics of geochemical tracers incorporated into its skeleton. To fill this knowledge gap, we compared skeletal δ¹⁸O signatures in live Diploastrea and Porites colonies from Southwest Lagoon, near Amédée Lighthouse, New Caledonia (at the southern latitudinal limit for Diploastrea) and Alor, Indonesia (in the core area of the Indo-Pacific Warm Pool). We designed a new microsampling technique to minimize smoothing and distortion of the isotopic records due to the complex calyx architecture and slow growth of Diploastrea. High-resolution isotope profiles from the septal portion of the Diploastrea corallite are attenuated, whereas those restricted to the central columella are similar in quality to those extracted from the well-established Porites coral archive. The δ¹⁸O-temperature relationship for the columellar portion of Diploastrea (−0.18‰/°C) is in good agreement with that derived for a nearby Porites (−0.19‰/°C; Quinn et al., 1996), on the basis of comparison with an in situ sea surface temperature record from Amédée Lighthouse. There is a measurable difference of 0.3 ± 0.1‰ between the kinetic/biological disequilibrium offsets from seawater δ¹⁸O composition for Diploastrea and Porites. Despite this offset in mean δ¹⁸O, Diploastrea accurately records the regional differences in mean temperature and salinity between New Caledonia and the Indo-Pacific Warm Pool. Additional tests show that Diploastrea records El Niño-Southern Oscillation (ENSO) interannual variability in sea surface temperature and salinity across the southwestern Pacific, indicating that it should yield dependable paleo-ENSO records. Based on these results, we propose that D. heliopora has the potential to provide an important new coral archive of tropical paleoclimate.  相似文献   

Nonracemic isovaline in the Murchison meteorite: chiral distribution and mineral association     

Sandra Pizzarello  Michael Zolensky 《Geochimica et cosmochimica acta》2003,67(8):1589-1595

The enantiomeric and carbon-isotopic composition of the amino acid isovaline have been analyzed in several samples of the Murchison meteorite and one sample of the Murray meteorite. l-Enantiomeric excesses of the amino acid were found to range from 0 to 15.2%, varying significantly both between meteorite stones and at short distances within a single stone. The upper limit of this range is the largest enantiomeric excess measured to date for a biologically rare meteoritic amino acid and raises doubts that circularly polarized light irradiation could have been the sole cause of amino acids chiral asymmetry in meteorites. Individual d- and l-isovaline δ¹³C values ware found to be about +18‰, with no significant differences between the two enantiomers to suggest terrestrial contamination. The amino acid relative abundance also varied between samples, with isovaline/alanine ratios of 0.5 to 6.5. X-ray diffraction analyses of contiguous meteorite fragments suggest a possible correlation between isovaline and hydrous silicates abundances.  相似文献   

Lead isotopic disequilibrium between sulfide and plagioclase in the bushveld complex and the chemical evolution of large layered intrusions     

E.A Mathez  T.E Waight 《Geochimica et cosmochimica acta》2003,67(10):1875-1888

The Pb isotopic compositions of coexisting plagioclase and sulfide from the Bushveld Complex were determined by laser ablation multi-collector ICPMS (LA MC-ICPMS). The samples are of the upper Critical Zone in the northeast corner of the Complex and were collected from drill core and underground mine exposures. All the rocks are fresh and exhibit no evidence for alteration, weathering, or disruption of the Pb isotope systematics subsequent to the initial cooling of the intrusion. Furthermore, individual plagioclase and sulfide crystals do not contain enough U to warrant correction for radiogenic in-growth. For these reasons, the measured Pb isotope ratios approximate the initial ones. For plagioclase, ²⁰⁷Pb/²⁰⁶Pb ranges from 0.98 to 1.02 and ²⁰⁸Pb/²⁰⁶Pb from 2.26 to 2.35. Low ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios characterize grain boundaries and partially annealed microcracks, some of which contain minute fragments of sulfide and other phases, and this accounts for most, if not all, the heterogeneity exhibited by individual samples. Real compositional differences exist, however, in plagioclase from different lithologic layers. For example, plagioclase ²⁰⁷Pb/²⁰⁶Pb values vary from 1.004 in norite beneath the Merensky pyroxenite to 1.009 in the mineralized pyroxenite, and 0.997 in overlying norite. In most samples in which sulfide and plagioclase coexist, the sulfide ²⁰⁷Pb/²⁰⁶Pb ratio is lower and ²⁰⁸Pb/²⁰⁶Pb ratio higher than the corresponding ones in plagioclase. For example, in a mineralized Merensky reef sample, average sulfide ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios are 0.993 and 2.313, respectively, while those in plagioclase are 1.000 and 2.292. In one sample, the sulfide is extremely heterogeneous, with ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios as low as 0.84 and 2.12. In this particular sample, the compositions must represent an isolated occurrence of addition of a young Pb component.The array of sulfide and plagioclase compositions requires multiple sources of Pb at the time of crystallization or soon thereafter. The disequilibrium between plagioclase and sulfide implies that some of the Pb originated from the isotopically distinct country rocks and was introduced at temperatures at which the composition of sulfide but not plagioclase could be modified. Thus, Bushveld sulfide, and to some extent plagioclase, do not reliably record the initial Pb isotopic composition(s) of the parent magma(s).  相似文献