137 research outputs found

    Spatial and Temporal Scales of Sverdrup Balance

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    Sverdrup balance underlies much of the theory of ocean circulation and provides a potential tool for describing the interior ocean transport from only the wind stress. Using both a model state estimate and an eddy-permitting coupled climate model, this study assesses to what extent and over what spatial and temporal scales Sverdrup balance describes the meridional transport. The authors find that Sverdrup balance holds to first order in the interior subtropical ocean when considered at spatial scales greater than approximately 5°. Outside the subtropics, in western boundary currents and at short spatial scales, significant departures occur due to failures in both the assumptions that there is a level of no motion at some depth and that the vorticity equation is linear. Despite the ocean transport adjustment occurring on time scales consistent with the basin-crossing times for Rossby waves, as predicted by theory, Sverdrup balance gives a useful measure of the subtropical circulation after only a few years. This is because the interannual transport variability is small compared to the mean transports. The vorticity input to the deep ocean by the interaction between deep currents and topography is found to be very large in both models. These deep transports, however, are separated from upper-layer transports that are in Sverdrup balance when considered over large scales

    X-ray Diffraction and Molecular Dynamics Study of Medium-range Order in Ambient and Hot Water

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    We have developed x-ray diffraction measurements with high energy-resolution and accuracy to study water structure at three different temperatures (7, 25 and 66 C) under normal pressure. Using a spherically curved Ge crystal an energy resolution better than 15 eV has been achieved which eliminates influence from Compton scattering. The high quality of the data allows a precise oxygen-oxygen pair correlation function (PCF) to be directly derived from the Fourier transform of the experimental data resolving shell structure out to ~12 {\AA}, i.e. 5 hydration shells. Large-scale molecular dynamics (MD) simulations using the TIP4P/2005 force-field reproduce excellently the experimental shell-structure in the range 4-12 {\AA} although less agreement is seen for the first peak in the PCF. The Local Structure Index [J. Chem. Phys. 104, 7671 (1996)] identifies a tetrahedral minority giving the intermediate-range oscillations in the PCF and a disordered majority providing a more featureless background in this range. The current study supports the proposal that the structure of liquid water, even at high temperatures, can be described in terms of a two-state fluctuation model involving local structures related to the high-density and low-density forms of liquid water postulated in the liquid-liquid phase transition hypothesis.Comment: Submitted to Phys. Chem. Chem. Phy

    Ab initio van der Waals interactions in simulations of water alter structure from mainly tetrahedral to high-density-like

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    The structure of liquid water at ambient conditions is studied in ab initio molecular dynamics simulations using van der Waals (vdW) density-functional theory, i.e. using the new exchange-correlation functionals optPBE-vdW and vdW-DF2. Inclusion of the more isotropic vdW interactions counteracts highly directional hydrogen-bonds, which are enhanced by standard functionals. This brings about a softening of the microscopic structure of water, as seen from the broadening of angular distribution functions and, in particular, from the much lower and broader first peak in the oxygen-oxygen pair-correlation function (PCF), indicating loss of structure in the outer solvation shells. In combination with softer non-local correlation terms, as in the new parameterization of vdW-DF, inclusion of vdW interactions is shown to shift the balance of resulting structures from open tetrahedral to more close-packed. The resulting O-O PCF shows some resemblance with experiment for high-density water (A. K. Soper and M. A. Ricci, Phys. Rev. Lett., 84:2881, 2000), but not directly with experiment for ambient water. However, an O-O PCF consisting of a linear combination of 70% from vdW-DF2 and 30% from experiment on low-density liquid water reproduces near-quantitatively the experimental O-O PCF for ambient water, indicating consistency with a two-liquid model with fluctuations between high- and low-density regions

    Disaccharide topology induces slow down in local water dynamics

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    Molecular level insight into water structure and structural dynamics near proteins, lipids and nucleic acids is critical to the quantitative understanding of many biophysical processes. Un- fortunately, understanding hydration and hydration dynamics around such large molecules is challenging because of the necessity of deconvoluting the effects of topography and chemical heterogeneity. Here we study, via classical all atom simulation, water structure and structural dynamics around two biologically relevant solutes large enough to have significant chemical and topological heterogeneity but small enough to be computationally tractable: the disaccharides Kojibiose and Trehalose. We find both molecules to be strongly amphiphilic (as quantified from normalized local density fluctuations) and to induce nonuniform local slowdown in water translational and rotational motion. Detailed analysis of the rotational slowdown shows that while the rotational mechanism is similar to that previously identified in other aqueous systems by Laage, Hynes and coworkers, two novel characteristics are observed: broadening of the transition state during hydrogen bond exchange (water rotation) and a subpopulation of water for which rotation is slowed because of hindered access of the new accepting water molecule to the transition state. Both of these characteristics are expected to be generic features of water rotation around larger biomolecules and, taken together, emphasize the difficulty in transferring insight into water rotation around small molecules to much larger amphiphilic solutes.This work is part of the research program of the “Stichting voor Fundamenteel Onderzoek der Materie (FOM)” which is financially supported by the “Nederlandse organisatie voor Wetenschap- pelijk Onderzoek (NWO)”. Further financial support was provided by a Marie Curie Incoming International Fellowship (RKC). We gratefully acknowledge SARA, the Dutch center for high- performance computing, for computational time and Huib Bakker and Daan Frenkel for useful critical reviews on an earlier version of this work. We thank two anonymous reviewers for their excellent work, especially for bringing to our attention calculations done on the transition state geometry of dimers and the overstructuring of the O-O radial distribution function of SPC/E water

    Individual, expected diameters of the ascending aorta and prevalence of dilations in a study-population aged 60-74 years:a DANCAVAS substudy

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    To determine individual, expected normal diameters of the ascending aorta (AAo) and prevalence of dilations based upon an absolute cut-off point (≥ 40 mm) and individual cut-off point (≥ 25% than expected normal). Non-contrast computed tomography (CT) scans were obtained in 14,993 individuals (95.0% male, mean age 67.8 ± 3.8). A sub-group (n = 291) had AAo diameter measured by transthoracic echocardiography. A prediction formula for AAo diameters was created from multivariate linear regression analysis based upon gender, age, and body surface area. An index was made by dividing observed diameters with predicted diameters. A size-index ≥ 1.25 was defined as dilated. Prevalence of AAo dilations among males and females using 40 mm as cut-off point were 10.6% and 2.1% (p &lt; 0.001), respectively, while 3.3% and 2.6% (p = 0.305) using the size-index ≥ 1.25, respectively. Proportion of agreement between cases of AAo dilations from the size-index and 40 mm was 93.0%. Using the size-index as 'golden standard' for dilation, the sensitivity and specificity using 40 mm as cut-off point for males were 100.0% and 92.4%, respectively, while 75.0% and 99.9%, respectively, for females. For males and females, the positive predicted values were 31.3% and 93.8%, respectively; the negative predicted values were 100.0% and 99.3%, respectively. An absolute echocardiographic size-criterion of 40 mm entails a significant number of females with missed AAo dilation, and a large number of males are mistaken to have dilated AAo. Thus, AAo diameters should be evaluated in relation to gender, age and BSA. This study provides a formula for potential clinical implementation.</p

    A review of the predictability and prediction of ENSO

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    A hierarchy of El Niño-Southern Oscillation (ENSO) prediction schemes has been developed during the Tropical Ocean-Global Atmosphere (TOGA) program which includes statistical schemes and physical models. The statistical models are, in general, based on linear statistical techniques and can be classified into models which use atmospheric (sea level pressure or surface wind) or oceanic (sea surface temperature or a measure of upper ocean heat content) quantities or a combination of oceanic and atmospheric quantities as predictors. The physical models consist of coupled ocean-atmosphere models of varying degrees of complexity, ranging from simplified coupled models of the “shallow water” type to coupled general circulation models. All models, statistical and physical, perform considerably better than the persistence forecast in predicting typical indices of ENSO on lead times of 6 to 12 months. The TOGA program can be regarded as a success from this perspective. However, despite the demonstrated predictability, little is known about ENSO predictability limits and the predictability of phenomena outside the tropical Pacific. Furthermore, the predictability of anomalous features known to be associated with ENSO (e.g., Indian monsoon and Sahel rainfall, southern African drought, and off-equatorial sea surface temperature) needs to be addressed in more detail. As well, the relative importance of different physical mechanisms (in the ocean or atmosphere) has yet to be established. A seasonal dependence in predictability is seen in many models, but the processes responsible for it are not fully understood, and its meaning is still a matter of scientific discussion. Likewise, a marked decadal variation in skill is observed, and the reasons for this are still under investigation. Finally, the different prediction models yield similar skills, although they are initialized quite differently. The reasons for these differences are also unclear
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