Density functional theory predictions of equilibrium isotope fractionation of iron due to redox changes and organic complexation     

Shawn D. Domagal-Goldman  James D. Kubicki 《Geochimica et cosmochimica acta》2008,72(21):5201-5216

We present molecular orbital/density functional theory (MO/DFT) calculations that predict a greater isotopic fractionation in redox reactions than in reactions involving ligand exchange. The predicted fractionation factors, reported as 1000·ln(^56-54α), associated with equilibrium between Fe-organic and Fe-H₂O species were <1.6‰ in vacuo and <1.2‰ in solution when the oxidation state of the system was held constant. These fractionation factors were significantly smaller than those predicted for equilibrium between different oxidation states of Fe, for which 1000·ln(^56-54α) was >2.7‰ in vacuo and >2.2‰ in solution when the bound ligands were unchanged. The predicted ⁵⁶Fe/⁵⁴Fe ratio was greater in complexes containing Fe³⁺ and in complexes with shorter Fe-O bond lengths; both of these trends follow previous theoretical results. Our predictions also agree with previous experimental measurements that suggest that the largest biological fractionations will be associated with processes that change the oxidation state of Fe, and that identification of biologically controlled Fe isotope fractionation may be difficult when abiotic redox fractionations are present in the system. The models studied here also have important implications for future theoretical isotope calculations, because we have discovered the necessity of using vibrational frequencies instead of reduced masses when predicting reduced partition functions in aqueous-phase species.  相似文献   

Uranophane dissolution and growth in CaCl₂-SiO₂(aq) test solutions     

James D. Prikryl 《Geochimica et cosmochimica acta》2008,72(18):4508-4520

The dissolution and growth of uranophane [Ca(UO₂)₂(SiO₃OH)₂·5H₂O] have been examined in Ca- and Si-rich test solutions at low temperatures (20.5 ± 2.0 °C) and near-neutral pH (∼6.0). Uranium-bearing experimental solutions undersaturated and supersaturated with uranophane were prepared in matrices of ∼10⁻² M CaCl₂ and ∼10⁻³ M SiO₂(aq). The experimental solutions were reacted with synthetic uranophane and analyzed periodically over 10 weeks. Interpretation of the aqueous solution data permitted extraction of a solubility constant for the uranophane dissolution reaction and standard state Gibbs free energy of formation for uranophane ( kJ mol⁻¹).  相似文献   

Crystal-Melt Separation and the Development of Isotopic Heterogeneities in Hybrid Magmas     

Beard  James S. 《Journal of Petrology》2008,49(5):1027-1041

If a magma is a hybrid of two (or more) isotopically distinctend-members, at least one of which is partially crystalline,separation of melt and crystals after hybridization will leadto the development of isotopic heterogeneities in the magmaas long as some of the pre-existing crystalline material (antecrysts)retains any of its original isotopic composition. This holdstrue whether the hybridization event is magma mixing as traditionallyconstrued, bulk assimilation, or melt assimilation. Once a magma-scaleisotopic heterogeneity is formed by crystal–melt separation,it is essentially permanent, persisting regardless of subsequentcrystallization, mixing, or equilibration events. The magnitudeof the isotopic variability resulting from crystal–meltseparation can be as large as that resulting from differentialcontamination, multiple isotopically distinct sources, or insitu isotopic evolution. In one model, a redistribution of one-thirdof the antecryst cargo yielded a crystal-enriched sample with⁸⁷Sr/⁸⁶Sr of 0·7058, whereas the complementary crystal-poorsample has ⁸⁷Sr/⁸⁶Sr of 0·7068. In other models, crystal-richsamples are enriched in radiogenic Sr. Isotopic heterogeneitiescan be either continuous (controlled by the modal distributionof crystals and melt) or discontinuous (when there is completeseparation of crystals and liquid). The first case may be exemplifiedby some isotopically zoned large-volume rhyolites, formed bythe eruptive inversion of a modally zoned magma chamber. Inthe latter case, the isotopic composition of any (for example)interstitial liquid will be distinct from the isotopic compositionof the bulk crystal fraction. The separation of such an interstitialliquid may explain the presence of isotopically distinct late-stageaplites in plutons. Crystal–melt separation provides anadditional option for the interpretation of isotopically zonedor heterogeneous magmas. This option is particularly attractivefor systems whose chemical variation is otherwise explicableby fractionation-dominated processes. Non-isotopic chemicalheterogeneities can also develop in this fashion. KEY WORDS: isotopic heterogeneity; zoning; hybrid magma; crystal separation; Sr isotopes; aplite; rhyolite  相似文献   

A CLASSIFICATION FOR THE SPATIAL ARRANGEMENT OF RURAL SETTLING PROJECTS: PIEDMONT HOMESTEAD PROJECT,GEORGIA     

James R. Bohland 《The Professional geographer》1968,20(3):187-194

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Acoustic-gravity wave propagation in an atmosphere with two sound channels     

Richard L. Pfeffer  James Zarichny 《Pure and Applied Geophysics》1963,55(1):175-199

Summary In order to interpret the observed features of pressure records produced by waves from large explosions in the earth's atmosphere, the writers have obtained numerical solutions of the homogeneous equations governing acoustic-gravity wave propagation in a stratified compressible fluid. Theoretical dispersion curves and variations of perturbation kinetic energy with altitude are presented for 11 normal modes. It is shown that the step-like character of the phase velocity curves in the velocity-period plane can be interpreted as being the result of interference between two families of normal modes-«quasi-horizontal modes» representing energy propagation in the lower atmosphere (below the ozonosphere) and «quasi-vertical modes» representing energy propagation in the upper atmosphere (above the ozonosphere). The theoretical prediction that several normal modes contribute to the observed barogram traces is verified by Fourier analysis of a number of wave records.Lamont Geological Observatory Contribution No. 611. — This research was supported by National Science Foundation Grant NSF-G-11997, Office of Naval Research Contract Nonr 266 (70), and National Science Foundation Grant NSF-GP-550. — Part of this research was done at the NASA Institute for Space Studies, New York, N. Y.  相似文献   

Evaluation of the Shepherd and Cushing (1980) model of density-dependent survival: a case study using striped bass (Morone saxatilis) larvae in the Potomac River, Maryland, USA     

Rutherford  Edward S; Rose  Kenneth A; Cowan  James H  Jr. 《ICES Journal of Marine Science》2003,60(6):1275-1287

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Distribution and relative abundance of harbour porpoises (Phocoena phocoena L.), white-beaked dolphins (Lagenorhynchus albirostris Gray), and minke whales (Balaenoptera acutorostrata Lacepede) around the British Isles     

Northridge  Simon P.; Tasker  Mark L.; Webb  Andrew; Williams  James M. 《ICES Journal of Marine Science》1995,52(1):55-66

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Sedimentary development of the Louisiana continental shelf related to sea level cycles: Part II—seismic response     

James M. Coleman  Harry H. Roberts 《Geo-Marine Letters》1988,8(2):109-119

Cyclic sequences occur worldwide in nearly every stratigraphic sequence; they are particularly well-developed in fluvial and deltaic sediments that have been influenced by high-frequency eustatic sea-level fluctuations. The large data base for this study (including 471 deep foundation borings, thousands of line kilometers of high-resolution seismic, and sedimentological and dating analyses) represents the most complete information on high-resolution chronostratigraphy and lithostratigraphy that is available on any modern continental shelf/upper slope. These data are used to document sedimentological characteristics and high-resolution seismic responses during three complete sea-level cycles over the entire continental shelf/upper slope of offshore Louisiana. Examination of high-resolution seismic records indicates that well-defined, high-amplitude, laterally continuous reflectors correlate with rising and high stand condensed sedimentary sequences and that the deposits laid down during falling and low-stand periods (expanded sections) are characterized by a wide range of acoustic responses. Discontinuous reflectors with high-amplitude variability, continuous parallel reflectors, and chaotic and amorphous zones are common acoustic responses. The association between a particular lithofacies and a specific acoustic response on 3.5-kHz records was found to be very poor.  相似文献   

Incorporation,distribution and fate of saturated petroleum hydrocarbons in sediments from a controlled marine ecosystem     

Terry L. Wade  James G. Quinn 《Marine environmental research》1980,3(1):15-33

A simulation of a chronic input of petroleum into an estuarine environment was investigated using the facilities at the Marine Ecosystems Research Laboratory at the University of Rhode Island. An oil-water dispersion of No. 2 fuel oil was added to the system (twice weekly for 24 weeks) and the saturated hydrocarbons from this oil were measured in suspended material and sediments. After the initial chronic oil addition, trace amounts of hydrocarbons were detected in the sediments within two weeks, but substantial accumulation was not detected for approximately 135 days. The oil appeared to enter the sediment via the suspended material, with most of the saturated hydrocarbons associated with smaller size sediment particles (< 45 μm to > 0·3 μm). With time, the fuel oil saturated hydrocarbons in the sediments were mixed to a depth of 3 to 4 cm. Although only 12% of the total saturated hydrocarbons added to the system were found in the sediments, these hydrocarbons appear to be relatively stable and were still detectable in these sediments for at least six months after the last oil addition.  相似文献   

Multi-decadal synthesis of benthic–pelagic coupling in the western arctic: Role of cross-shelf advective processes     

Kenneth H. Dunton  Jonathan L. Goodall  Susan V. Schonberg  Jacqueline M. Grebmeier  David R. Maidment 《Deep Sea Research Part II: Topical Studies in Oceanography》2005,52(24-26):3462

Using geographic information systems (GIS) software and geostatistical techniques, we utilized three decades of water-column chlorophyll a data to examine the relative importance of autochthonous versus allochthonous sources of reduced carbon to benthic communities that occur from the northern Bering to the eastern Beaufort Sea shelf. Spatial trend analyses revealed areas of high benthic biomass (>300 g m⁻²) and chlorophyll (>150 mg m⁻²) on both the southern and northern Chukchi shelf; both areas are known as depositional centers for reduced organic matter that originates on the Bering Sea shelf and is advected northward in Anadyr and Bering shelf water masses. We found a significant correlation between biomass and chlorophyll a in the Chukchi Sea, reflective of the strong benthic–pelagic coupling in a system that is utilized heavily by benthic-feeding marine mammals. In contrast, there was no significant correlation between biomass and chlorophyll in the Beaufort Sea, which by comparison, is considerably less productive (biomass and chlorophyll, <75 g m⁻² and <50 mg m⁻², respectively). One notable exception is an area of relatively high biomass (50–100 g m⁻²) and chlorophyll (80 mg m⁻²) near Barter Island in the eastern Beaufort Sea. Compared to other adjacent areas in the Beaufort Sea, the chlorophyll values in the vicinity of Barter Island were considerably higher and likely reflect a long-hypothesized upwelling in that area and close coupling between the benthos and autochthonous production. In the Bering Sea, a drop in benthic biomass in 1994 compared with previous measurements (1974–1993) may support earlier observations that document a decline in biomass that began between the 1980s and 1990s in the Chirikov Basin and south of St. Lawrence Island. The results of this study indicate that the benthos is an excellent long-term indicator of both local and physical advective processes. In addition, this work provides further evidence that secondary production on arctic shelves can be significantly augmented by reduced carbon advected from highly productive adjacent shelves.  相似文献