Vapor pressures and evaporation coefficients for melts of ferromagnesian chondrule-like compositions     

A.V. Fedkin  L. Grossman  M.S. Ghiorso 《Geochimica et cosmochimica acta》2006,70(1):206-223

To determine evaporation coefficients for the major gaseous species that evaporate from silicate melts, the Hertz-Knudsen equation was used to model the compositions of residues of chondrule analogs produced by evaporation in vacuum by Hashimoto [Hashimoto A. (1983) Evaporation metamorphism in the early solar nebula-evaporation experiments on the melt FeO-MgO-SiO₂-CaO-Al₂O₃ and chemical fractionations of primitive materials. Geochem. J. 17, 111-145] and Wang et al. [Wang J., Davis A. M., Clayton R. N., Mayeda T. K., Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO₂-CaO-Al₂O₃-TiO₂ rare earth element melt system. Geochim. Cosmochim. Acta 65, 479-494], in vacuum and in H₂ by Yu et al. [Yu Y., Hewins R. H., Alexander C. M. O’D., Wang J. (2003) Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts. Geochim. Cosmochim. Acta 67, 773-786], and in H₂ by Cohen et al. [Cohen B. A., Hewins R. H., Alexander C. M. O’D. (2004) The formation of chondrules by open-system melting of nebular condensates. Geochim. Cosmochim. Acta 68, 1661-1675]. Vapor pressures were calculated using the thermodynamic model of Ghiorso and Sack [Ghiorso M. S., Sack R. O. (1995) Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures. Contrib. Mineral. Petrol. 119, 197-212], except for the late, FeO-free stages of the Wang et al. (2001) and Cohen et al. (2004) experiments, where the CMAS activity model of Berman [Berman R. G. (1983) A thermodynamic model for multicomponent melts, with application to the system CaO-MgO-Al₂O₃-SiO₂. Ph.D. thesis, University of British Columbia] was used. From these vapor pressures, evaporation coefficients (α) were obtained that give the best fits to the time variation of the residue compositions. Evaporation coefficients derived for Fe_(g), Mg_(g), and SiO_(g) from the Hashimoto (1983) experiments are similar to those found by Alexander [Alexander C. M. O’D. (2004) Erratum. Meteoritics Planet. Sci. 39, 163] in his EQR treatment of the same data and also adequately describe the FeO-bearing stages of the Wang et al. (2001) experiments. From the Yu et al. (2003) experiments at 1723 K, α_Na = 0.26 ± 0.05, and α_K = 0.13 ± 0.02 in vacuum, and α_Na = 0.042 ± 0.020, andα_K = 0.017 ± 0.002 in 9 × 10⁻⁵ bar H₂. In the FeO-free stages of the Wang et al. (2001) experiments, α_Mg and α_SiO are significantly different from their respective values in the FeO-bearing portions of the same experiments and from the vacuum values obtained at the same temperature by Richter [Richter F. M., Davis A. M., Ebel D. S., Hashimoto A. (2002) Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta 66, 521-540] for CMAS compositions much lower in MgO. When corrected for temperature, the values of α_Mg and α_SiO that best describe the FeO-free stages of the Wang et al. (2001) experiments also adequately describe the FeO-free stage of the Cohen et al. (2004) H₂ experiments, but α_Fe that best describes the FeO-bearing stage of the latter experiment differs significantly from the temperature-corrected value derived from the Hashimoto (1983) vacuum data.  相似文献   

Cs and Cl NMR spectroscopy and molecular dynamics modeling of Cs and Cl complexation with natural organic matter     

Xiang Xu 《Geochimica et cosmochimica acta》2006,70(17):4319-4331

Interaction of dissolved aqueous species with natural organic matter (NOM) is thought to be important in sequestering some species and enhancing the transport of others, but little is known about these interactions on a molecular scale. This paper describes a combined experimental ¹³³Cs and ³⁵Cl nuclear magnetic resonance (NMR) and computational molecular dynamics (MD) modeling study of the interaction of Cs⁺ and Cl⁻ with Suwannee River NOM. The results provide a detailed picture of the molecular-scale structure and dynamics of these interactions. Individual NOM molecules are typically hundreds to thousands of Daltons in weight, and on the molecular scale their interaction with small dissolved species can be investigated in ways similar to those used to study the interaction of dissolved aqueous species with mineral surfaces. As for such surface interactions, understanding both the structural environments and the dynamics over a wide range of frequencies is essential. The NMR results show that Cs⁺ is associated with NOM at pH values from 3.4 ± 0.5 (unbuffered Suwannee River NOM solution) to 9.0 ± 0.5. The extent of interaction increases with decreasing CsCl concentration at constant pH. It also decreases with increasing pH at constant CsCl concentration due to pH-dependent negative structural charge development on the NOM caused by progressive deprotonation of carboxylic and phenolic groups. The presence of NOM has little effect on the ¹³³Cs chemical shifts, demonstrating that its local coordination environment does not change significantly due to interaction with the NOM. Narrow, solution-like line widths indicate rapid exchange of Cs⁺ between the NOM and bulk solution at frequencies of >10² Hz. The MD simulations support these results and show that Cs⁺ is associated with the NOM principally as outer sphere complexes and that this interaction does not reduce the Cs⁺ diffusion coefficient sufficiently to cause NMR line broadening. The ³⁵Cl NMR data and the MD results are consistent in demonstrating that there is no significant complexation between Cl⁻ and NOM in the pH range investigated, consistent with negative structural charge on the NOM.  相似文献   

Tracing nitrogen in volcanic and geothermal volatiles from the Nicaraguan volcanic front     

L.J. Elkins  T.P. Fischer  Z.D. Sharp  J. Walker 《Geochimica et cosmochimica acta》2006,70(20):5215-5235

We report new chemical and isotopic data from 26 volcanic and geothermal gases, vapor condensates, and thermal water samples, collected along the Nicaraguan volcanic front. The samples were analyzed for chemical abundances and stable isotope compositions, with a focus on nitrogen abundances and isotope ratios. These data are used to evaluate samples for volatile contributions from magma, air, air-saturated water, and the crust. Samples devoid of crustal contamination (based upon He isotope composition) but slightly contaminated by air or air-saturated water are corrected using N₂/Ar ratios in order to obtain primary magmatic values, composed of contributions from upper mantle and subducted hemipelagic sediment on the down-going plate. Using a mantle endmember with δ¹⁵N = −5‰ and N₂/He = 100 and a subducted sediment component with δ¹⁵N = +7‰ and N₂/He = 10,500, the average sediment contribution to Nicaraguan volcanic and geothermal gases was determined to be 71%. Most of the gases were dominated by sediment-derived nitrogen, but gas from Volcán Mombacho, the southernmost sampling location, had a mantle signature (46% from subducted sediment, or 54% from the mantle) and an affinity with mantle-dominated gases discharging from Costa Rica localities to the south. High CO₂/N_{2 exc.} ratios (N_{2 exc.} is the N₂ abundance corrected for contributions from air) in the south are similar to those in Costa Rica, and reflect the predominant mantle wedge input, whereas low ratios in the north indicate contribution by altered oceanic crust and/or preferential release of nitrogen over carbon from the subducting slab. Sediment-derived nitrogen fluxes at the Nicaraguan volcanic front, estimated by three methods, are 7.8 × 10⁸ mol N/a from ³He flux, 6.9 × 10⁸ mol/a from SO₂ flux, and 2.1 × 10⁸ and 1.3 × 10⁹ mol/a from CO₂ fluxes calculated from ³He and SO₂, respectively. These flux results are higher than previous estimates for Central America, reflecting the high sediment-derived volatile contribution and the high nitrogen content of geothermal and volcanic gases in Nicaragua. The fluxes are also similar to but higher than estimated hemipelagic nitrogen inputs at the trench, suggesting addition of N from altered oceanic basement is needed to satisfy these flux estimates. The similarity of the calculated input of N via the trench to our calculated outputs suggests that little or none of the subducted nitrogen is being recycled into the deeper mantle, and that it is, instead, returned to the surface via arc volcanism.  相似文献   

Moving Geochemical Transactions forward as an open access journal     

Martin AA Schoonen  Ken B Anderson  Scott A Wood 《Geochemical transactions》2006,7(1):1-2

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Channel water balance of the Lena River Cascade system     

N. E. Kosheleva  E. B. Karabanov  N. S. Kasimov  A. G. Kositskii  V. A. Bychinskii  D. Williams  S. Armstrong 《Doklady Earth Sciences》2006,411(2):1452-1456

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Apparent seasonal variations in iron photoreduction in acidic discharge from a former pyrite mine,Oakland, California     

《Applied Geochemistry》2006,21(7):1109-1122

This study investigates a watershed influenced by acid mine drainage emanating from the former Leona Heights Sulfur Mine, located in Oakland, California. The primary factors that temporally controlled the magnitude of iron photoreduction included initial iron concentration, incident ultraviolet radiation, water temperature, biotic oxidation, flow rates, and the Fe(III) species present. Vegetation was not expected to seasonally influence the amount of incoming solar radiation reaching the water surface as the tree canopy contained significant cover during both the April and July monitoring events. Accordingly, it was anticipated that iron photoreduction would be greatest during the summer when both incoming ultraviolet radiation and dissolved iron were at a maximum. This was, however, not the case. A substantial decline in the apparent magnitude of iron photoreduction occurred during the summer/dry season (July) with respect to measurements taken during the spring/wet season (April). The primary reasons for the observed phenomenon were attributed to factors which may seasonally control the physical presence of iron oxidizing bacteria at the site and water temperature, which influences the optimum rate of bacterially mediated iron oxidation.  相似文献   

The Sevsk woolly mammoth (Mammuthus primigenius) site in Russia: Taphonomic,biological and behavioral interpretations     

《Quaternary International》2006

Excavations at Sevsk, Bryansk Region, Russia, by the Paleontological Institute of the Russian Academy of Sciences in 1988–1991 recovered 3800 bones of woolly mammoth (Mammuthus primigenius Blum.) representing a minimum of 33 individuals. The locality is one of the largest naturally occurring deposits of mammoth remains in Europe and is inferred to be a catastrophic death assemblage. The material includes five skeletons of juvenile mammoths, from 1 month to 6 or 7 years of age, as well as partial skeletons and isolated bones of adult individuals. A femur and humerus of an approximately 10–12-month-old fetus are also among the finds. Morphological features suggest that the Sevsk mammoths belonged to one family group; the age structure and sexual composition of the assemblage do not differ significantly from that of a family group of Modern African elephants. In contrast to other localities in Siberia and central Russia, relatively more (about 45% of individuals) prepubertal animals are preserved at Sevsk. Radiocarbon dates indicate that the mammoths died about 14,000 years ago. Data from diatoms, pollen and rodents, as well as archeological evidence, corroborate this age, and provide the basis for a paleoenvironmental reconstruction at the end of the Valdaian Glaciation in western Russia.  相似文献   

Middle Weichselian environments on western Yamal Peninsula, Kara Sea based on pollen records     

Andrei A. Andreev  Steven L. Forman  William F. Manley 《Quaternary Research》2006,65(2):275-281

Pollen data from two sections from a coastal cliff on the western Yamal Peninsula (69°43.27′N, 66°48.80′E) document the environmental history during the Karginsky (Middle Weichselian) interstadial. Low pollen concentrations, high amounts of redeposited pollen, and relatively high presence of Artemisia pollen characterize sediments deposited at about 33,000 ¹⁴C yr B.P. Grass-sedge plant associations with few other herbs occupied the area during the late Karginsky interstadial. Artemisia pollen may indicate rather xerophytic vegetation and disturbed soils in the area. The dominance of redeposited pollen reflects scarce (disturbed) vegetation cover and low pollen productivity. The climate was relatively cold and dry. Sediments dated to 32,400 ¹⁴C yr B.P. contain fewer redeposited pollen and concentration of non-redeposited pollen is significantly higher. Pollen contents indicate the dominance of tundra-like grass-sedge vegetation and more humid conditions. Pollen records dated between 30,100 and 25,100 ¹⁴C yr B.P. also reflect scarce tundra-like vegetation during this interval. The presence of Betula nana and Salix pollen may reflect limited presence of shrub communities. This suggests that the climate was somewhat warmer during the latter part of the interstadial. However, generally the pollen records show that harsh environmental conditions prevailed on the Yamal Peninsula during the Karginsky interstadial.  相似文献   

Equation of state of MgGeO3 perovskite to 65 GPa: comparison with the post-perovskite phase     

C. E. Runge  A. Kubo  B. Kiefer  Y. Meng  V. B. Prakapenka  G. Shen  R. J. Cava  T. S. Duffy 《Physics and Chemistry of Minerals》2006,33(10):699-709

The equation of state of MgGeO₃ perovskite was determined between 25 and 66 GPa using synchrotron X-ray diffraction with the laser-heated diamond anvil cell. The data were fit to a third-order Birch–Murnaghan equation of state and yielded a zero-pressure volume (V ₀) of 182.2 ± 0.3 Å³ and bulk modulus (K ₀) of 229 ± 3 GPa, with the pressure derivative (K′₀ = (?K ₀/?P) _T ) fixed at 3.7. Differential stresses were evaluated using lattice strain theory and found to be typically less than about 1.5 GPa. Theoretical calculations were also carried out using density functional theory from 0 to 205 GPa. The equation of state parameters from theory (V ₀ = 180.2 Å³, K ₀ = 221.3 GPa, and K′₀ = 3.90) are in agreement with experiment, although theoretically calculated volumes are systematically lower than experiment. The properties of the perovskite phase were compared to MgGeO₃ post-perovskite phase near the observed phase transition pressure (～65 GPa). Across the transition, the density increased by 2.0(0.7)%. This is in excellent agreement with the theoretically determined density change of 1.9%; however both values are larger than those for the (Mg,Fe)SiO₃ phase transition. The bulk sound velocity change across the transition is small and is likely to be negative [?0.5(1.6)% from experiment and ?1.2% from theory]. These results are similar to previous findings for the (Mg,Fe)SiO₃ system. A linearized Birch–Murnaghan equation of state fit to each axis yielded zero-pressure compressibilities of 0.0022, 0.0009, and 0.0016 GPa^?1 for the a, b, and c axis, respectively. Magnesium germanate appears to be a good analog system for studying the properties of the perovskite and post-perovskite phases in silicates.  相似文献   

Urban lightning climatology and GIS: An analytical framework from the case study of Atlanta, Georgia     

J. Anthony Stallins  Mace L. Bentley 《Applied geography (Sevenoaks, England)》2006,26(3-4):242-259

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