Flux comparison of Eulerian and Lagrangian estimates of Agulhas leakage: A case study using a numerical model

Estimating the magnitude of Agulhas leakage, the volume flux of water from the Indian to the Atlantic Ocean, is difficult because of the presence of other circulation systems in the Agulhas region. Indian Ocean water in the Atlantic Ocean is vigorously mixed and diluted in the Cape Basin. Eulerian integration methods, where the velocity field perpendicular to a section is integrated to yield a flux, have to be calibrated so that only the flux by Agulhas leakage is sampled. Two Eulerian methods for estimating the magnitude of Agulhas leakage are tested within a high-resolution two-way nested model with the goal to devise a mooring-based measurement strategy. At the GoodHope line, a section halfway through the Cape Basin, the integrated velocity perpendicular to that line is compared to the magnitude of Agulhas leakage as determined from the transport carried by numerical Lagrangian floats. In the first method, integration is limited to the flux of water warmer and more saline than specific threshold values. These threshold values are determined by maximizing the correlation with the float-determined time series. By using the threshold values, approximately half of the leakage can directly be measured. The total amount of Agulhas leakage can be estimated using a linear regression, within a 90% confidence band of 12 Sv. In the second method, a subregion of the GoodHope line is sought so that integration over that subregion yields an Eulerian flux as close to the float-determined leakage as possible. It appears that when integration is limited within the model to the upper 300 m of the water column within 900 km of the African coast the time series have the smallest root-mean-square difference. This method yields a root-mean-square error of only 5.2 Sv but the 90% confidence band of the estimate is 20 Sv. It is concluded that the optimum thermohaline threshold method leads to more accurate estimates even though the directly measured transport is a factor of two lower than the actual magnitude of Agulhas leakage in this model.

Relating Agulhas leakage to the Agulhas Current retroflection location

The relation between the Agulhas Current retroflection location and the magnitude of Agulhas leakage, the transport of water from the Indian to the Atlantic Ocean, is investigated in a high-resolution numerical ocean model. Sudden eastward retreats of the Agulhas Current retroflection loop are linearly related to the shedding of Agulhas rings, where larger retreats generate larger rings. Using numerical Lagrangian floats a 37 year time series of the magnitude of Agulhas leakage in the model is constructed. The time series exhibits large amounts of variability, both on weekly and annual time scales. A linear relation is found between the magnitude of Agulhas leakage and the location of the Agulhas Current retroflection, both binned to three month averages. In the relation, a more westward location of the Agulhas Current retroflection corresponds to an increased transport from the Indian Ocean to the Atlantic Ocean. When this relation is used in a linear regression and applied to almost 20 years of altimetry data, it yields a best estimate of the mean magnitude of Agulhas leakage of 13.2 Sv. The early retroflection of 2000, when Agulhas leakage was probably halved, can be identified using the regression.

A weaker Agulhas Current leads to more Agulhas leakage

Time series of transports in the Agulhas region have been constructed by simulating Lagrangian drifter trajectories in a 1/10 degree two-way nested ocean model. Using these 34 year long time series it is shown that smaller (larger) Agulhas Current transport leads to larger (smaller) Indian-Atlantic inter-ocean exchange. When transport is low, the Agulhas Current detaches farther downstream from the African continental slope. Moreover, the lower inertia suppresses generation of anti-cyclonic vorticity. These two effects cause the Agulhas retroflection to move westward and enhance Agulhas leakage. In the model a 1 Sv decrease in Agulhas Current transport at 32°S results in a 0.7 ± 0.2 Sv increase in Agulhas leakage.

A study by high energy transfer inelastic neutron scattering spectroscopy of the mineral fraction of ox femur bone

We have used high energy transfer (HET) inelastic neutron scattering spectroscopy to measure the vibrational modes in the spectra of hydroxyapatite, bone and brushite to confirm our earlier work that only a fraction of the hydroxyl groups in bone mineral are substituted. The HET spectra are better observed due to the higher scattering cross section of hydrogen compared with the other elements in the calcium phosphate compounds. (C) 2003 Elsevier Science B.V. All rights reserved.

LDA or GGA? A combined experimental inelastic neutron scattering and ab initio lattice dynamics study of alkali metal hydrides

In a previous work, we carried out inelastic neutron scattering (INS) spectroscopy experiments and preliminary first principles calculations on alkali metal hydrides. The complete series of alkali metal hydrides, LiH, NaH, KH, RbH and CsH was measured in the high-resolution TOSCA INS spectrometer at ISIS. Here, we present the results of ab initio electronic structure calculations of the properties of the alkali metal hydrides using both the local density approximation (LDA) and the generalized gradient approximation (GGA), using the Perdew–Burke–Ernzerhof (PBE) parameterization. Properties calculated were lattice parameters, bulk moduli, dielectric constants, effective charges, electronic densities and inelastic neutron scattering (INS) spectra. We took advantage of the currently available computer power to use full lattice dynamics theory to calculate thermodynamic properties for these materials. For the alkali metal hydrides (LiH, NaH, KH, RbH and CsH) using lattice dynamics, we found that the INS spectra calculated using LDA agreed better with the experimental data than the spectra calculated using GGA. Both zero-point effects and thermal contributions to free energies had an important effect on INS and several thermodynamic properties.

Pressure effects revealed by small angle neutron scattering on block copolymer gels

We study the effects of hydrostatic pressure (P) on aqueous solutions and gels of the block copolymer B20E610 (E, oxyethylene; B, oxybutylene; subscripts, number of repeats), by performing simultaneous small angle neutron scattering/pressure experiments. Micellar cubic gels were studied for 9.5 and 4.5 wt% B20E610 at T = 20-80 and 35-55 degrees C, respectively, while micellar isotropic solutions where Studied for 4.5 wt% B20E610 at T > 55 degrees C. We observed that the interplanar distance d(110) (cubic unit cell parameter a = root 2d(110)) decreases while the correlation length of the Cubic order (delta) increases, upon increasing P at a fixed T for 9.5 wt% B20E610. The construction of master Curves for d(110) and delta corresponding to 9.5 wt% B20E610 proved the correlation between changes in T and P. Neither d(110) and delta nor the cubic-isotropic phase transition temperature was affected by the applied pressure for 4.5 wt% B20E610. The dramatic contrast between the pressure-induced behavior observed for 9.5 and 4.5 wt% B20E610 suggests that pressure induced effects might be more effectively transmitted through samples that present wider domains of cubic structure order (9.5 wt% compared to 4.5 wt% B20E610).

Molecular aluminum hydrides identified by inelastic neutron scattering during H-2 regeneration of catalyst-doped NaAlH4

Catalyst-doped sodium aluminum hydrides have been intensively studied as solid hydrogen carriers for onboard proton-exchange membrane (PEM) fuel cells. Although the importance of catalyst choice in enhancing kinetics for both hydrogen uptake and release of this hydride material has long been recognized, the nature of the active species and the mechanism of catalytic action are unclear. We have shown by inelastic neutron scattering (INS) spectroscopy that a volatile molecular aluminum hydride is formed during the early stage of H-2 re-eneration of a depleted, catalyst-doped sodium aluminum hydride. Computational modeling of the INS spectra suggested the formation of AlH3 and oligomers (AlH3)(n) (Al2H6, Al3H9, and Al4H12 clusters), which are pertinent to the mechanism of hydrogen storage. This paper demonstrates, for the first time, the existence of these volatile species.

Structure of AuCN determined from total neutron diffraction

The structure of gold cyanide, AuCN, has been determined at 10 and 300 K using total neutron diffraction. The structure consists of infinite -Au-(CN)-Au-(CN)-Au-(CN)- linear chains, hexagonally packed, with the gold atoms in sheets. The Au-C and Au-N bond lengths are found to be identical, with d(Au-C/N) = 1.9703(5) Angstrom at 300 K. This work supersedes a previous study, by others, which used Rietveld analysis of neutron Bragg diffraction in isolation, and found these bonds to have significantly different lengths (Deltad = 0.24 Angstrom) at 300 K. The total correlation function, T(r), at 10 and 300 K, has been modeled using information derived from total diffraction. The broadening of inter- and intrachain correlations differs markedly due to random displacements of the chains in the direction of the chain axes. This is a consequence of the relatively weak bonding between the chains. An explanation for the negative thermal expansion in the c-direction, which occurs between 10 and 300 K, is presented.

Modeling the structure of amorphous MoS3: a neutron diffraction and reverse Monte Carlo study

A model for the structure of amorphous molybdenum trisulfide, a-MoS3, has been created using reverse Monte Carlo methods. This model, which consists of chains Of MoS6 units sharing three sulfurs with each of its two neighbors and forming alternate long, nonbonded, and short, bonded, Mo-Mo separations, is a good fit to the neutron diffraction data and is chemically and physically realistic. The paper identifies the limitations of previous models based on Mo-3 triangular clusters in accounting for the available experimental data.

Inelastic neutron scattering in spectroscopic studies of hydrogen on carbon-supported catalysts-experimental spectra and computed spectra of model systems

Inelastic neutron scattering spectroscopy has been used to observe and characterise hydrogen on the carbon component of a Pt/C catalyst. INS provides the complete vibration spectrum of coronene, regarded as a molecular model of a graphite layer. The vibrational modes are assigned with the aid of ab initio density functional theory calculations and the INS spectra by the a-CLIMAX program. A spectrum for which the H modes of coronene have been computationally suppressed, a carbon-only coronene spectrum, is a better representation of the spectrum of a graphite layer than is coronene itself. Dihydrogen dosing of a Pt/C catalyst caused amplification of the surface modes of carbon, an effect described as H riding on carbon. From the enhancement of the low energy carbon modes (100-600 cm(-1)) it is concluded that spillover hydrogen becomes attached to dangling bonds at the edges of graphitic regions of the carbon support. (C) 2003 Elsevier Science B.V. All rights reserved.