Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)(6)(3-/4-) redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 mu m diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of k(mt) > 0.01 m s(-1) (or k(mt) > 1.0 cm s(-1)) are observed at 50 mu m diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 mu m diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 mu m diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme-modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)63–/4– redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 µm diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of kmt > 0.01 m s–1(or kmt > 1.0 cm s–1) are observed at 50 µm diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 µm diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 µm diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Ocean acoustic models for low frequency propagation in 2D and 3D environments

In this paper we are mainly concerned with the development of efficient computer models capable of accurately predicting the propagation of low-to-middle frequency sound in the sea, in axially symmetric (2D) and in fully 3D environments. The major physical features of the problem, i.e. a variable bottom topography, elastic properties of the subbottom structure, volume attenuation and other range inhomogeneities are efficiently treated. The computer models presented are based on normal mode solutions of the Helmholtz equation on the one hand, and on various types of numerical schemes for parabolic approximations of the Helmholtz equation on the other. A new coupled mode code is introduced to model sound propagation in range-dependent ocean environments with variable bottom topography, where the effects of an elastic bottom, of volume attenuation, surface and bottom roughness are taken into account. New computer models based on finite difference and finite element techniques for the numerical solution of parabolic approximations are also presented. They include an efficient modeling of the bottom influence via impedance boundary conditions, they cover wide angle propagation, elastic bottom effects, variable bottom topography and reverberation effects. All the models are validated on several benchmark problems and versus experimental data. Results thus obtained were compared with analogous results from standard codes in the literature.

On the relationship between the Indian summer monsoon and river flow in the Aral Sea basin

We study the contemporaneous relationship between the intensity of the Indian Summer Monsoon (ISM) and runoff in the major rivers of the Aral Sea basin (Amudarya, Syrdarya) and some of their subcatchments. To this end, we use All-India rainfall (AIR) data, CRU surface observations of precipitation and temperature, ERA40 atmospheric data, and natural discharge data corrected for human interference. We show that there is a highly significant positive correlation between ISM intensity and Amudarya runoff. This finding cannot be explained by the spill-over of ISM precipitation over the Hindu Kush into the Amudarya basin. Instead, we suggest that the observed co-variability is mediated by tropospheric temperature variations due to fluctuations in the ISM intensity. These variations are known to be due to Rossby-wave propagation in response to condensational heating during monsoon precipitation. We hypothesise that the corresponding anomalies in surface temperatures imply anomalies in meltwater formation.

Wave trapping in a two-dimensional sound-soft or sound-hard acoustic waveguide of slowly-varying width

In this paper we derive novel approximations to trapped waves in a two-dimensional acoustic waveguide whose walls vary slowly along the guide, and at which either Dirichlet (sound-soft) or Neumann (sound-hard) conditions are imposed. The guide contains a single smoothly bulging region of arbitrary amplitude, but is otherwise straight, and the modes are trapped within this localised increase in width. Using a similar approach to that in Rienstra (2003), a WKBJ-type expansion yields an approximate expression for the modes which can be present, which display either propagating or evanescent behaviour; matched asymptotic expansions are then used to derive connection formulae which bridge the gap across the cut-off between propagating and evanescent solutions in a tapering waveguide. A uniform expansion is then determined, and it is shown that appropriate zeros of this expansion correspond to trapped mode wavenumbers; the trapped modes themselves are then approximated by the uniform expansion. Numerical results determined via a standard iterative method are then compared to results of the full linear problem calculated using a spectral method, and the two are shown to be in excellent agreement, even when $\epsilon$, the parameter characterising the slow variations of the guide’s walls, is relatively large.

Plane wave approximation in linear elasticity

We consider the approximation of solutions of the time-harmonic linear elastic wave equation by linear combinations of plane waves. We prove algebraic orders of convergence both with respect to the dimension of the approximating space and to the diameter of the domain. The error is measured in Sobolev norms and the constants in the estimates explicitly depend on the problem wavenumber. The obtained estimates can be used in the h- and p-convergence analysis of wave-based finite element schemes.

Internal wave drag in stratified flow over mountains on a beta plane

The impact of the variation of the Coriolis parameter f on the drag exerted by internal Rossby-gravity waves on elliptical mountains is evaluated using linear theory, assuming constant wind and static stability and a beta-plane approximation. Previous calculations of inertia-gravity wave drag are thus extended in an attempt to establish a connection with existing studies on planetary wave drag, developed primarily for fluids topped by a rigid lid. It is found that the internal wave drag for zonal westerly flow strongly increases relative to that given by the calculation where f is assumed to be a constant, particularly at high latitudes and for mountains aligned meridionally. Drag increases with mountain width for sufficiently wide mountains, reaching values much larger than those valid in the non-rotating limit. This occurs because the drag receives contributions from a low wavenumber range, controlled by the beta effect, which accounts for the drag amplification found here. This drag amplification is shown to be considerable for idealized analogues of real mountain ranges, such as the Himalayas and the Rocky mountains, and comparable to the barotropic Rossby wave drag addressed in previous studies.

Linear criteria for gravity-wave breaking in resonant stratified flow over a ridge

Using linear theory, it is shown that, in resonant flow over a 2D mountain ridge, such as exists when a layer of uniform wind is topped by an environmental critical level, the conditions for internal gravity-wave breaking are different from those determined in previous studies for non-resonant flows. For Richardson numbers in the shear layer not exceeding 2.25, two zones of flow overturning exist, respectively below and downstream and above and upstream of the expected locations. Flow overturning occurs for values of the dimensionless height of the ridge smaller than those required for a uniform wind profile. These results may have implications for the physical understanding of high-drag states.

Importance of oceanic resolution and mean state on the extra-tropical response to El Niño in a matrix of coupled models

The extra-tropical response to El Niño in configurations of a coupled model with increased horizontal resolution in the oceanic component is shown to be more realistic than in configurations with a low resolution oceanic component. This general conclusion is independent of the atmospheric resolution. Resolving small-scale processes in the ocean produces a more realistic oceanic mean state, with a reduced cold tongue bias, which in turn allows the atmospheric model component to be forced more realistically. A realistic atmospheric basic state is critical in order to represent Rossby wave propagation in response to El Niño, and hence the extra-tropical response to El Niño. Through the use of high and low resolution configurations of the forced atmospheric-only model component we show that, in isolation, atmospheric resolution does not significantly affect the simulation of the extra-tropical response to El Niño. It is demonstrated, through perturbations to the SST forcing of the atmospheric model component, that biases in the climatological SST field typical of coupled model configurations with low oceanic resolution can account for the erroneous atmospheric basic state seen in these coupled model configurations. These results highlight the importance of resolving small-scale oceanic processes in producing a realistic large-scale mean climate in coupled models, and suggest that it might may be possible to “squeeze out” valuable extra performance from coupled models through increases to oceanic resolution alone.

Wave-activity conservation laws for the three-dimensional anelastic and Boussinesq equations with a horizontally homogeneous background flow

Wave-activity conservation laws are key to understanding wave propagation in inhomogeneous environments. Their most general formulation follows from the Hamiltonian structure of geophysical fluid dynamics. For large-scale atmospheric dynamics, the Eliassen–Palm wave activity is a well-known example and is central to theoretical analysis. On the mesoscale, while such conservation laws have been worked out in two dimensions, their application to a horizontally homogeneous background flow in three dimensions fails because of a degeneracy created by the absence of a background potential vorticity gradient. Earlier three-dimensional results based on linear WKB theory considered only Doppler-shifted gravity waves, not waves in a stratified shear flow. Consideration of a background flow depending only on altitude is motivated by the parameterization of subgrid-scales in climate models where there is an imposed separation of horizontal length and time scales, but vertical coupling within each column. Here we show how this degeneracy can be overcome and wave-activity conservation laws derived for three-dimensional disturbances to a horizontally homogeneous background flow. Explicit expressions for pseudoenergy and pseudomomentum in the anelastic and Boussinesq models are derived, and it is shown how the previously derived relations for the two-dimensional problem can be treated as a limiting case of the three-dimensional problem. The results also generalize earlier three-dimensional results in that there is no slowly varying WKB-type requirement on the background flow, and the results are extendable to finite amplitude. The relationship A E =cA P between pseudoenergy A E and pseudomomentum A P, where c is the horizontal phase speed in the direction of symmetry associated with A P, has important applications to gravity-wave parameterization and provides a generalized statement of the first Eliassen–Palm theorem.

Coupled Kelvin-wave and mirage-wave instabilities in semigeostrophic dynamics

A weak instability mode, associated with phase-locked counterpropagating coastal Kelvin waves in horizontal anticyclonic shear, is found in the semigeostrophic (SG) equations for stratified flow in a channel. This SG instability mode approximates a similar mode found in the Euler equations in the limit in which particle-trajectory slopes are much smaller than f/N, where f is the Coriolis frequency and N > f the buoyancy frequency. Though weak under normal parameter conditions, this instability mode is of theoretical interest because its existence accounts for the failure of an Arnol’d-type stability theorem for the SG equations. In the opposite limit, in which the particle motion is purely vertical, the Euler equations allow only buoyancy oscillations with no horizontal coupling. The SG equations, on the other hand, allow a physically spurious coastal “mirage wave,” so called because its velocity field vanishes despite a nonvanishing disturbance pressure field. Counterpropagating pairs of these waves can phase-lock to form a spurious “mirage-wave instability.” Closer examination shows that the mirage wave arises from failure of the SG approximations to be self-consistent for trajectory slopes f/N.