The counter-propagating Rossby-wave perspective on baroclinic instability. Part IV: Nonlinear life cycles

Pairs of counter-propagating Rossby waves (CRWs) can be used to describe baroclinic instability in linearized primitive-equation dynamics, employing simple propagation and interaction mechanisms at only two locations in the meridional plane—the CRW ‘home-bases’. Here, it is shown how some CRW properties are remarkably robust as a growing baroclinic wave develops nonlinearly. For example, the phase difference between upper-level and lower-level waves in potential-vorticity contours, defined initially at the home-bases of the CRWs, remains almost constant throughout baroclinic wave life cycles, despite the occurrence of frontogenesis and Rossby-wave breaking. As the lower wave saturates nonlinearly the whole baroclinic wave changes phase speed from that of the normal mode to that of the self-induced phase speed of the upper CRW. On zonal jets without surface meridional shear, this must always act to slow the baroclinic wave. The direction of wave breaking when a basic state has surface meridional shear can be anticipated because the displacement structures of CRWs tend to be coherent along surfaces of constant basic-state angular velocity, U. This results in up-gradient horizontal momentum fluxes for baroclinically growing disturbances. The momentum flux acts to shift the jet meridionally in the direction of the increasing surface U, so that the upper CRW breaks in the same direction as occurred at low levels

New perspectives on the Northern Hemisphere winter storm tracks

The aim of this paper is to explore the use of both an Eulerian and system-centered method of storm track diagnosis applied to a wide range of meteorological fields at multiple levels to provide a range of perspectives on the Northern Hemisphere winter transient motions and to give new insight into the storm track organization and behavior. The data used are primarily from the European Centre for Medium-Range Weather Forecasts reanalyses project extended with operational analyses to the period 1979-2000. This is supplemented by data from the National Centers for Environmental Prediction and Goddard Earth Observing System 1 reanalyses. The range of fields explored include the usual mean sea level pressure and the lower- and upper-tropospheric height, meridional wind, vorticity, and temperature, as well as the potential vorticity (PV) on a 330-K isentropic surface (PV330) and potential temperature on a PV = 2 PVU surface (theta(PV2)). As well as reporting the primary analysis based on feature tracking, the standard Eulerian 2-6-day bandpass filtered variance analysis is also reported and contrasted with the tracking diagnostics. To enable the feature points to be identified as extrema for all the chosen fields, a planetary wave background structure is removed at each data time. The bandpass filtered variance derived from the different fields yield a rich picture of the nature and comparative magnitudes of the North Pacific and Atlantic storm tracks, and of the Siberian and Mediterranean candidates for storm tracks. The feature tracking allows the cyclonic and anticyclonic activities to be considered seperately. The analysis indicates that anticyclonic features are generally much weaker with less coherence than the cyclonic systems. Cyclones and features associated with them are shown to have much greater coherence and give tracking diagnostics that create a vivid storm track picture that includes the aspects highlighted by the variances as well as highlighting aspects that are not readily available from Eulerian studies. In particular, the upper-tropospheric features as shown by negative theta(PV2), for example, occur in a band spiraling around the hemisphere from the subtropical North Atlantic eastward to the high latitudes of the same ocean basin. Lower-troposphere storm tracks occupy more limited longitudinal sectors, with many of the individual storms possibly triggered from the upper-tropospheric disturbances in the spiral band of activity.

Life-cycle simulations of shallow frontal waves and the impact of deformation strain

The life-cycle of shallow frontal waves and the impact of deformation strain on their development is investigated using the idealised version of the Met Office non-hydrostatic Unified Model which includes the same physics and dynamics as the operational forecast model. Frontal wave development occurs in two stages; first, a deformation strain is applied to a front and a positive potential vorticity (PV) strip forms, generated by latent heat release in the frontal updraft; second, as the deformation strain is reduced the PV strip breaks up into individual anomalies. The circulations associated with the PV anomalies cause shallow frontal waves to form. The structure of the simulated frontal waves is consistent with the conceptual model of a frontal cyclone. Deeper frontal waves are simulated if the stability of the atmosphere is reduced. Deformation strain rates of different strengths are applied to the PV strip to determine whether a deformation strain threshold exists above which frontal wave development is suppressed. An objective method of frontal wave activity is defined and frontal wave development was found to be suppressed by deformation strain rates $\ge 0.4\times10^{-5}\mbox{s}^{-1}$. This value compares well with observed deformation strain rate thresholds and the analytical solution for the minimum deformation strain rate needed to suppress barotropic frontal wave development. The deformation strain rate threshold is dependent on the strength of the PV strip with strong PV strips able to overcome stronger deformation strain rates (leading to frontal wave development) than weaker PV strips.

Velocities of compressional and shear waves in limestones

Carbonate rocks are important hydrocarbon reservoir rocks with complex textures and petrophysical properties (porosity and permeability) mainly resulting from various diagenetic processes (compaction, dissolution, precipitation, cementation, etc.). These complexities make prediction of reservoir characteristics (e.g. porosity and permeability) from their seismic properties very difficult. To explore the relationship between the seismic, petrophysical and geological properties, ultrasonic compressional- and shear-wave velocity measurements were made under a simulated in situ condition of pressure (50 MPa hydrostatic effective pressure) at frequencies of approximately 0.85 MHz and 0.7 MHz, respectively, using a pulse-echo method. The measurements were made both in vacuum-dry and fully saturated conditions in oolitic limestones of the Great Oolite Formation of southern England. Some of the rocks were fully saturated with oil. The acoustic measurements were supplemented by porosity and permeability measurements, petrological and pore geometry studies of resin-impregnated polished thin sections, X-ray diffraction analyses and scanning electron microscope studies to investigate submicroscopic textures and micropores. It is shown that the compressional- and shear-wave velocities (V-p and V-s, respectively) decrease with increasing porosity and that V-p decreases approximately twice as fast as V-s. The systematic differences in pore structures (e.g. the aspect ratio) of the limestones produce large residuals in the velocity versus porosity relationship. It is demonstrated that the velocity versus porosity relationship can be improved by removing the pore-structure-dependent variations from the residuals. The introduction of water into the pore space decreases the shear moduli of the rocks by about 2 GPa, suggesting that there exists a fluid/matrix interaction at grain contacts, which reduces the rigidity. The predicted Biot-Gassmann velocity values are greater than the measured velocity values due to the rock-fluid interaction. This is not accounted for in the Biot-Gassmann velocity models and velocity dispersion due to a local flow mechanism. The velocities predicted by the Raymer and time-average relationships overestimated the measured velocities even more than the Biot model.

Carboxylate anions binding and sensing by a novel tetraazamacrocycle containing ferrocene as receptor

A tetraazamacrocycle containing ferrocene moieties has been synthesized and characterized. The tetraprotonated form of this compound was evaluated as a receptor (R) for anion recognition of several substrates (S), Cl-, PF6-, HSO4-, H2PO4- and carboxylates, such as p-nitrobenzoate (p-nbz(-)), phthalate (ph(2-)), isophthalate (iph(2-)) and dipicolinate (dipic(2-)). H-1 NMR titrations in CD3OD indicated that this receptor is not suitable for recognizing HSO4- and H2PO4-, but weakly binds p-nbz(-), and strongly interacts with ph(2-), dipic(2-), and iph(2-) anions forming 1 : 2 assembled species. The largest beta(2) binding constant was determined for ph(2-), followed by dipic(2-) and finally iph(2-). The effect of the anionic substrates on the electron-transfer process of the ferrocene units of R was evaluated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in methanol solution and 0.1 mol dm(-3) (CH3)(4)NCl as the supporting electrolyte. Titrations of the receptor were undertaken by addition of anion solutions in their tetrabutylammonium or tetramethylammonium forms. The protonated ligand exhibits a reversible voltammogram, which shifts cathodically in the presence of the substrates. The data revealed kinetic constraints in the formation of the receptor/substrate entity for dipic(2-), ph(2-) and iph(2-) anions, but not for p-nbz(-). In spite of the slow kinetics of assembled species formation with the ph(2-) substrate, this anion provides the largest redox-response when the supramolecular entity is formed, followed by dipic(2-), iph(2-) and finally p-nbz(-) anions. This trend is in agreement with the H-1 NMR results and the values of the binding constants. Single crystal X-ray structures of the receptor with PF6-, ph(2-), iph(2-) and p-nbz(-) were carried out and showed that supermolecules with a RS2 stoichiometry are formed with the first three anions, but RS4 with p-nbz(-). In all cases the binding occurs outside the macrocyclic cavity via N-H center dot center dot center dot O=C hydrogen bonds for carboxylate anions and N - H center dot center dot center dot F hydrogen bonds for the PF6- anion, which is in agreement with the solution results. The macrocyclic framework adopts different conformations in order to interact with each substrate having Fe center dot center dot center dot Fe intramolecular distances ranging from 10.125(14) to 12.783(15) angstrom.

Post-partum depression and infant growth in a South African peri-urban settlement

Aim: To examine the association between maternal post-natal depression and infant growth. Background: Infant growth has recently been shown, in two studies from South Asia, to be adversely affected by maternal depression in the early post-partum period. It is uncertain whether a similar association obtains in developing countries outside Asia. Method: A sample of 147 mother–infant dyads was recruited from a peri-urban settlement outside Cape Town and seen at 2 and 18 months post partum. Results: No clear effect of post-partum depression on infant growth was found. Although maternal depression at 2 months was found to be associated with lower infant weight at 18 months, when birthweight was considered this effect disappeared. Conclusions: Possible explanations for the non-replication of the South Asian findings are considered.

Effect of improving representation of horizontal and vertical cloud structure on the Earth's global radiation budget. Part II: The global effects

Reliably representing both horizontal cloud inhomogeneity and vertical cloud overlap is fundamentally important for the radiation budget of a general circulation model. Here, we build on the work of Part One of this two-part paper by applying a pair of parameterisations that account for horizontal inhomogeneity and vertical overlap to global re-analysis data. These are applied both together and separately in an attempt to quantify the effects of poor representation of the two components on radiation budget. Horizontal inhomogeneity is accounted for using the “Tripleclouds” scheme, which uses two regions of cloud in each layer of a gridbox as opposed to one; vertical overlap is accounted for using “exponential-random” overlap, which aligns vertically continuous cloud according to a decorrelation height. These are applied to a sample of scenes from a year of ERA-40 data. The largest radiative effect of horizontal inhomogeneity is found to be in areas of marine stratocumulus; the effect of vertical overlap is found to be fairly uniform, but with larger individual short-wave and long-wave effects in areas of deep, tropical convection. The combined effect of the two parameterisations is found to reduce the magnitude of the net top-of-atmosphere cloud radiative forcing (CRF) by 2.25 W m−2, with shifts of up to 10 W m−2 in areas of marine stratocumulus. The effects of the uncertainty in our parameterisations on radiation budget is also investigated. It is found that the uncertainty in the impact of horizontal inhomogeneity is of order ±60%, while the uncertainty in the impact of vertical overlap is much smaller. This suggests an insensitivity of the radiation budget to the exact nature of the global decorrelation height distribution derived in Part One.

Mono- and heterodimetallic FeII and RuII complexes based on a novel heteroditopic 4′-{bis(phosphanyl)aryl}-2,2′:6′,2″-terpyridine ligand

In the search for a versatile building block that allows the preparation of heteroditopic tpy-pincer bridging ligands, the synthon 14'-[C6H3(CH2Br)(2)-3,5]-2,2':6',2 ''-terpyridine was synthesized. Facile introduction of diphenylphosphanyl groups in this synthon gave the ligand 14'-[C6H3(CH2PPh2)2-3,5]-2,2':6',2"-terpyridine) ([tpyPC(H)Pj). The asymmetric mononuclear complex [Fe(tpy){tpyPC(H)P}](PF6)(2), prepared by selective coordination of [Fe(tpy)Cl-3] to the tpy moiety of [tpyPC(H)P], was used for the synthesis of the heterodimetallic complex [Fe(tpy)(tpyPCP)Ru(tpy)](PFC,)3, which applies the "complex as ligand" approach. Coordination of the ruthenium centre at the PC(H)P-pincer moiety of [Fe(tpy){tpyPC(H)P}](PF6)(2) has been achieved by applying a transcyclometallation procedure. The ground-state electronic properties of both complexes, investigated by cyclic and square-wave voltammetries and UV/Vis spectroscopy, are discussed and compared with those of [Fe(tPY)(2)](PF6)(2) and [Ru(PCP)(tpy)]Cl, which represent the mononuclear components of the heterodinuclear species. An in situ UV/Vis spectroelectrochemical study was performed in order to localize the oxidation and reduction steps and to gain information about the Fe-II-Ru-II communication in the heterodimetallic system [Fe(tpy)(tpyPCP)Ru(tpy)](PF6)(3) mediated by the bridging ligand [tpyPCP]. Both the voltammetric and spectroelectrochemical results point to only very limited electronic interaction between the metal centres in the ground state.

Dietary prebiotics: current status and new definition

In November 2008, a group of scientists met at the 6th Meeting of the International Scientific Association of Probiotics and Prebiotics (ISAPP) in London, Ontario, Canada, to discuss the functionality of prebiotics. As a result of this, it was concluded that the prebiotic field is currently dominated by gastrointestinal events. However, in the future, it may be the case that other mixed microbial ecosystems may be modulated by a prebiotic approach, such as the oral cavity, skin and the urogenital tract. Therefore, a decision was taken to build upon the current prebiotic status and define a niche for ‘dietary prebiotics’. This review is co-authored by the working group of ISAPP scientists and sets the background for defining a dietary prebiotic as ‘‘a selectively fermented ingredient that results in specific changes in the composition and/or activity of the gastrointestinal microbiota, thus conferring benefit(s) upon host health’’.

Water vapour self-continuum and water dimers: 1. Analysis of recent work

Recent laboratory observations and advances in theoretical quantum chemistry allow a reappraisal of the fundamental mechanisms that determine the water vapour self-continuum absorption throughout the infrared and millimetre wave spectral regions. By starting from a framework that partitions bimolecular interactions between water molecules into free-pair states, true bound and quasi-bound dimers, we present a critical review of recent observations, continuum models and theoretical predictions. In the near-infrared bands of the water monomer, we propose that spectral features in recent laboratory-derived self-continuum can be well explained as being due to a combination of true bound and quasi-bound dimers, when the spectrum of quasi-bound dimers is approximated as being double the broadened spectrum of the water monomer. Such a representation can explain both the wavenumber variation and the temperature dependence. Recent observations of the self-continuum absorption in the windows between these near-infrared bands indicate that widely used continuum models can underestimate the true strength by around an order of magnitude. An existing far-wing model does not appear able to explain the discrepancy, and although a dimer explanation is possible, currently available observations do not allow a compelling case to be made. In the 8–12 micron window, recent observations indicate that the modern continuum models either do not properly represent the temperature dependence, the wavelength variation, or both. The temperature dependence is suggestive of a transition from the dominance of true bound dimers at lower temperatures to quasibound dimers at higher temperatures. In the mid- and far-infrared spectral region, recent theoretical calculations indicate that true bound dimers may explain at least between 20% and 40% of the observed self-continuum. The possibility that quasi-bound dimers could cause an additional contribution of the same size is discussed. Most recent theoretical considerations agree that water dimers are likely to be the dominant contributor to the self-continuum in the mm-wave spectral range.

Rigid ferrocenophane and its metal complexes with transition and alkaline-earth metal ions

The rigid [6]ferrocenophane, L-1, was synthesised by condensation of 1,1'-ferrocene dicarbaldehyde with trans-1,2-diaminocyclohexane in high dilution at r.t. followed by reduction. When other experimental conditions were employed, the [6,6,6]ferrocenephane (L-2) was also obtained. Both compounds were characterised by single crystal X-ray crystallography. The protonation of L-1 and its metal complexation were evaluated by the effect on the electron-transfer process of the ferrocene (fc) unit of L-1 using cyclic voltammetry (CV) and square wave voltammetry (SWV) in anhydrous CH3CN solution and in 0.1 M (Bu4NPF6)-Bu-n as the supporting electrolyte. The electrochemical process of L-1 between 300 and 900 mV is complicated by amine oxidation. On the other hand, an anodic shift from the fc/fc(+) wave of L-1 of 249, 225, 81 and 61 mV was observed by formation of Zn2+, Ni2+, Pd2+ and Cu2+ complexes, respectively. Whereas Mg2+ and Ca2+ only have with L-1 weak interactions and they promote the acid-base equilibrium of L-1. This reveals that L-1 is an interesting molecular redox sensor for detection of Zn2+ and Ni2+, although the kinetics of the Zn2+ complex formation is much faster than that of the Ni2+ one. The X-ray crystal structure of [(PdLCl2)-Cl-1] was determined and showed a square-planar environment with Pd(II) and Fe(II) centres separated by 3.781(1) angstrom. The experimental anodic shifts were elucidated by DFT calculations on the [(MLCl2)-Cl-1] series and they are related to the nature of the HOMO of these complexes and a four-electron, two-orbital interaction.

Cloud statistics and cloud radiative effect for a low-mountain site

In 2007, the Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) was operated for a nine-month period in the Murg Valley, Black Forest, Germany, in support of the Convective and Orographically-induced Precipitation Study (COPS). The synergy of AMF and COPS partner instrumentation was exploited to derive a set of high-quality thermodynamic and cloud property profiles with 30 s resolution. In total, clouds were present 72% of the time, with multi-layer mixed phase (28.4%) and single-layer water clouds (11.3%) occurring most frequently. A comparison with the Cloudnet sites Chilbolton and Lindenberg for the same time period revealed that the Murg Valley exhibits lower liquid water paths (LWPs; median = 37.5 g m−2) compared to the two sites located in flat terrain. In order to evaluate the derived thermodynamic and cloud property profiles, a radiative closure study was performed with independent surface radiation measurements. In clear sky, average differences between calculated and observed surface fluxes are less than 2% and 4% for the short wave and long wave part, respectively. In cloudy situations, differences between simulated and observed fluxes, particularly in the short wave part, are much larger, but most of these can be related to broken cloud situations. The daytime cloud radiative effect (CRE), i.e. the difference of cloudy and clear-sky net fluxes, has been analysed for the whole nine-month period. For overcast, single-layer water clouds, sensitivity studies revealed that the CRE uncertainty is likewise determined by uncertainties in liquid water content and effective radius. For low LWP clouds, CRE uncertainty is dominated by LWP uncertainty; therefore refined retrievals, such as using infrared and/or higher microwave frequencies, are needed.

Plane wave discontinuous Galerkin methods for the 2D Helmholtz equation: analysis of the $p$-version

Plane wave discontinuous Galerkin (PWDG) methods are a class of Trefftz-type methods for the spatial discretization of boundary value problems for the Helmholtz operator $-\Delta-\omega^2$, $\omega>0$. They include the so-called ultra weak variational formulation from [O. Cessenat and B. Després, SIAM J. Numer. Anal., 35 (1998), pp. 255–299]. This paper is concerned with the a priori convergence analysis of PWDG in the case of $p$-refinement, that is, the study of the asymptotic behavior of relevant error norms as the number of plane wave directions in the local trial spaces is increased. For convex domains in two space dimensions, we derive convergence rates, employing mesh skeleton-based norms, duality techniques from [P. Monk and D. Wang, Comput. Methods Appl. Mech. Engrg., 175 (1999), pp. 121–136], and plane wave approximation theory.

The zero, the centre and the empty utopia: from Rossellini to Walter Salles

This article examines utopian gestures and inaugural desires in two films which became symbolic of the Brazilian Film Revival in the late 1990s: Central Station (1998) and Midnight (1999). Both evolve around the idea of an overcrowded or empty centre in a country trapped between past and future, in which the motif of the zero stands for both the announcement and the negation of utopia. The analysis draws parallels between them and new wave films which also elaborate on the idea of the zero, with examples picked from Italian neo-realism, the Brazilian Cinema Novo and the New German Cinema. In Central Station, the ‘point zero’, or the core of the homeland, is retrieved in the archaic backlands, where political issues are resolved in the private sphere and the social drama turns into family melodrama. Midnight, in its turn, recycles Glauber Rocha’s utopian prophecies in the new millennium’s hour zero, when the earthly paradise represented by the sea is re-encountered by the middle-class character, but not by the poor migrant. In both cases, public injustice is compensated by the heroes’ personal achievements, but those do not refer to the real nation, its history or society. Their utopian breadth, based on nostalgia, citation and genre techniques, is of a virtual kind, attune to cinema only.