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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 1779-1790 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: X-ray absorption spectroscopy is widely employed in the structural analysis of disordered systems. In the standard extended x-ray absorption fine structure (EXAFS) analysis the coordination of the photoabsorber is usually defined by means of Gaussian shells. It is known that this procedure can lead to significant errors in the determination of the coordination parameters for systems which present anharmonic thermal vibrations or interatomic asymmetric pair distribution functions. An efficient method has been recently employed in the study of the hydration shells of bromide and rubidium ions and brominated hydrocarbon molecules in diluted aqueous solutions. According to this method, pair distribution functions [g(r)] obtained from molecular dynamics simulations can be used as relevant models in the calculation of the EXAFS signals. Moreover, asymmetric shells modeled on the g(r) first peaks, have been employed in the EXAFS analysis and the parameters defining the asymmetric peaks have been optimized during the minimization procedure. In the present paper this new procedure has been used to investigate the coordination of Br− in methanol. The analysis of this system is particularly interesting due to the presence of three well separated coordination shells. We show that the inclusion of the hydrogen signal is essential to perform a reliable analysis. A comparison of the analysis with asymmetric and Gaussian shells shows how the accuracy of the EXAFS data analysis is improved by using asymmetric shells. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Publication Date: 2010-05-10
    Description: A watermass-based framework is presented for a quantitative understanding of the processes controlling the cycling of carbon in the Southern Ocean. The approach is developed using a model simulation of the global carbon transports within the ocean and with the atmosphere. It is shown how the watermass framework sheds light on the interplay between biology, air-sea gas exchange, and internal ocean transport including diapycnal processes, and the way in which this interplay controls the large-scale ocean-atmosphere carbon exchange. The simulated pre-industrial regional patterns of DIC distribution and the global distribution of the pre-industrial air-sea CO2 fluxes compare well with other model results and with results from an ocean inversion method. The main differences are found in the Southern Ocean where the model presents a stronger CO2 outgassing south of the polar front, a result of the upwelling of DIC-rich deep waters into the surface layer. North of the subantarctic front the typical temperature-driven solubility effect produces a net ingassing of CO2. The biological controls on surface CO2 fluxes through primary production is generally smaller than the temperature effect on solubility. Novel to this study is also a Lagrangian trajectory analysis of the meridional transport of DIC. The analysis allows to evaluate the contribution of separate branches of the global thermohaline circulation (identified by watermasses) to the vertical distribution of DIC throughout the Southern Ocean and towards the global ocean. The most important new result is that the overturning associated with Subantarctic Mode Waters sustains a northward net transport of DIC (15.7×107 mol/s across 30° S). This new finding, which has also relevant implications on the prediction of anthropogenic carbon redistribution, results from the specific mechanism of SAMW formation and its source waters whose consequences on tracer transports are analyzed for the first time in this study.
    Print ISSN: 1810-6277
    Electronic ISSN: 1810-6285
    Topics: Biology , Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 3
    Publication Date: 2011-05-04
    Description: The scientific motivation for this study is to understand the processes in the ocean interior controlling carbon transfer across 30° S. To address this, we have developed a unified framework for understanding the interplay between physical drivers such as buoyancy fluxes and ocean mixing, and carbon-specific processes such as biology, gas exchange and carbon mixing. Given the importance of density in determining the ocean interior structure and circulation, the framework is one that is organized by density and water masses, and it makes combined use of Eulerian and Lagrangian diagnostics. This is achieved through application to a global ice-ocean circulation model and an ocean biogeochemistry model, with both components being part of the widely-used IPSL coupled ocean/atmosphere/carbon cycle model. Our main new result is the dominance of the overturning circulation (identified by water masses) in setting the vertical distribution of carbon transport from the Southern Ocean towards the global ocean. A net contrast emerges between the role of Subantarctic Mode Water (SAMW), associated with large northward transport and ingassing, and Antarctic Intermediate Water (AAIW), associated with a much smaller export and outgassing. The differences in their export rate reflects differences in their water mass formation processes. For SAMW, two-thirds of the surface waters are provided as a result of the densification of thermocline water (TW), and upon densification this water carries with it a substantial diapycnal flux of dissolved inorganic carbon (DIC). For AAIW, principal formatin processes include buoyancy forcing and mixing, with these serving to lighten CDW. An additional important formation pathway of AAIW is through the effect of interior processing (mixing, including cabelling) that serve to densify SAMW. A quantitative evaluation of the contribution of mixing, biology and gas exchange to the DIC evolution per water mass reveals that mixing and, secondarily, gas exchange, effectively nearly balance biology on annual scales (while the latter process can be dominant at seasonal scale). The distribution of DIC in the northward flowing water at 30° S is thus primarily set by the DIC values of the water masses that are involved in the formation processes.
    Print ISSN: 1726-4170
    Electronic ISSN: 1726-4189
    Topics: Biology , Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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