Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study

A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, nBu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [nBu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV–vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc+, followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO22+. NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8]4– is delocalized over all NCS– ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8]4– (An = Th, U) and [UO2(NCS)5]3– has been explored by a combination of DFT and QTAIM analysis, and the U–N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)–NCS ion is more ionic than what was found for U(IV)–Cl complexes.

Language in genetic syndromes and cognitive modularity

In recent years, research into the impact of genetic abnormalities on cognitive development, including language, has become recognized for its potential to make valuable contributions to our understanding of the brain–behaviour relationships underlying language acquisition as well as to understanding the cognitive architecture of the human mind. The publication of Fodor’s ( 1983 ) book The Modularity of Mind has had a profound impact on the study of language and the cognitive architecture of the human mind. Its central claim is that many of the processes involved in comprehension are undertaken by special brain systems termed ‘modules’. This domain specificity of language or modularity has become a fundamental feature that differentiates competing theories and accounts of language acquisition (Fodor 1983 , 1985 ; Levy 1994 ; Karmiloff-Smith 1998 ). However, although the fact that the adult brain is modularized is hardly disputed, there are different views of how brain regions become specialized for specific functions. A question of some interest to theorists is whether the human brain is modularized from the outset (nativist view) or whether these distinct brain regions develop as a result of biological maturation and environmental input (neuroconstructivist view). One source of insight into these issues has been the study of developmental disorders, and in particular genetic syndromes, such as Williams syndrome (WS) and Down syndrome (DS). Because of their uneven profiles characterized by dissociations of different cognitive skills, these syndromes can help us address theoretically significant questions. Investigations into the linguistic and cognitive profiles of individuals with these genetic abnormalities have been used as evidence to advance theoretical views about innate modularity and the cognitive architecture of the human mind. The present chapter will be organized as follows. To begin, two different theoretical proposals in the modularity debate will be presented. Then studies of linguistic abilities in WS and in DS will be reviewed. Here, the emphasis will be mainly on WS due to the fact that theoretical debates have focused primarily on WS, there is a larger body of literature on WS, and DS subjects have typically been used for the purposes of comparison. Finally, the modularity debate will be revisited in light of the literature review of both WS and DS. Conclusions will be drawn regarding the contribution of these two genetic syndromes to the issue of cognitive modularity, and in particular innate modularity.

Development of a wind gust model to estimate gust speeds and their return periods

Spatially dense observations of gust speeds are necessary for various applications, but their availability is limited in space and time. This work presents an approach to help to overcome this problem. The main objective is the generation of synthetic wind gust velocities. With this aim, theoretical wind and gust distributions are estimated from 10 yr of hourly observations collected at 123 synoptic weather stations provided by the German Weather Service. As pre-processing, an exposure correction is applied on measurements of the mean wind velocity to reduce the influence of local urban and topographic effects. The wind gust model is built as a transfer function between distribution parameters of wind and gust velocities. The aim of this procedure is to estimate the parameters of gusts at stations where only wind speed data is available. These parameters can be used to generate synthetic gusts, which can improve the accuracy of return periods at test sites with a lack of observations. The second objective is to determine return periods much longer than the nominal length of the original time series by considering extreme value statistics. Estimates for both local maximum return periods and average return periods for single historical events are provided. The comparison of maximum and average return periods shows that even storms with short average return periods may lead to local wind gusts with return periods of several decades. Despite uncertainties caused by the short length of the observational records, the method leads to consistent results, enabling a wide range of possible applications.

Solar wind-magnetosphere coupling functions on timescales of 1 day to 1 year

There are no direct observational methods for determining the total rate at which energy is extracted from the solar wind by the magnetosphere. In the absence of such a direct measurement, alternative means of estimating the energy available to drive the magnetospheric system have been developed using different ionospheric and magnetospheric indices as proxies for energy consumption and dissipation and thus the input. The so-called coupling functions are constructed from the parameters of the interplanetary medium, as either theoretical or empirical estimates of energy transfer, and the effectiveness of these coupling functions has been evaluated in terms of their correlation with the chosen index. A number of coupling functions have been studied in the past with various criteria governing event selection and timescale. The present paper contains an exhaustive survey of the correlation between geomagnetic activity and the near-Earth solar wind and two of the planetary indices at a wide variety of timescales. Various combinations of interplanetary parameters are evaluated with careful allowance for the effects of data gaps in the interplanetary data. We show that the theoretical coupling, P�, function first proposed by Vasyliunas et al. is superior at all timescales from 1-day to 1-year.

A multipoint study of a substorm occurring on 7 December, 1992, and its theoretical implications

On 7 December 1992, a moderate substorm was observed by a variety of satellites and ground-based instruments. Ionospheric flows were monitored near dusk by the Goose Bay HF radar and near midnight by the EISCAT radar. The observed flows are compared here with magnetometer observations by the IMAGE array in Scandinavia and the two Greenland chains, the auroral distribution observed by Freja and the substorm cycle observations by the SABRE radar, the SAMNET magnetometer array and LANL geosynchronous satellites. Data from Galileo Earth-encounter II are used to estimate the IMF B-z component. The data presented show that the substorm onset electrojet at midnight was confined to closed field lines equatorward of the preexisting convection reversal boundaries observed in the dusk and midnight regions. No evidence of substantial closure of open flux was detected following this substorm onset. Indeed the convection reversal boundary on the duskside continued to expand equatorward after onset due to the continued presence of strong southward IMF, such that growth and expansion phase features were simultaneously present. Clear indications of closure of open flux were not observed until a subsequent substorm intensification 25 min after the initial onset. After this time, the substorm auroral bulge in the nightside hours propagated well poleward of the pre-existing convection reversal boundary, and strong flow perturbations were observed by the Goose Bay radar, indicative of flows driven by reconnection in the tail.

Earth's magnetospheric cusps

Earth's cusps are magnetic field features in the magnetosphere associated with regions through which plasma from the Sun can have direct access to the upper atmosphere. Recently, new ground-based observations, combined with in situ satellite measurements, have led the way in reinterpreting cusp signatures. These observations, combined with theoretical advances, have stimulated new interest in the solar wind-magnetosphere-ionosphere coupling chain. This coupling process is important because it causes both momentum and energy from the solar wind to enter into the near-Earth region. Here we describe the current ideas concerning the cusps and the supporting observational evidence which have evolved over the past 30 years. We include discussion on the plasma entry process, particle motion between the magnetopause and ionosphere, ground optical and radar measurements, and transient events. We also review the important questions that remain to be answered.

Dependence of convective flows and particle precipitation in the high-latitude dayside ionosphere on theXandYcomponents of the interplanetary magnetic field

The asymmetries in the convective flows, current systems, and particle precipitation in the high-latitude dayside ionosphere which are related to the equatorial plane components of the interplanetary magnetic field (IMF) are discussed in relation to the results of several recent observational studies. It is argued that all of the effects reported to date which are ascribed to the y component of the IMF can be understood, at least qualitatively, in terms of a simple theoretical picture in which the effects result from the stresses exerted on the magnetosphere consequent on the interconnection of terrestrial and interplanetary fields. In particular, relaxation under the action of these stresses allows, in effect, a partial penetration of the IMF into the magnetospheric cavity, such that the sense of the expected asymmetry effects on closed field lines can be understood, to zeroth order, in terms of the “dipole plus uniform field” model. In particular, in response to IMF By, the dayside cusp should be displaced in longitude about noon in the same sense as By in the northern hemisphere, and in the opposite sense to By in the southern hemisphere, while simultaneously the auroral oval as a whole should be shifted in the dawn-dusk direction in the opposite sense with respect to By. These expected displacements are found to be consistent with recently published observations. Similar considerations lead to the suggestion that the auroral oval may also undergo displacements in the noon-midnight direction which are associated with the x component of the IMF. We show that a previously published study of the position of the auroral oval contains strong initial evidence for the existence of this effect. However, recent results on variations in the latitude of the cusp are more ambiguous. This topic therefore requires further study before definitive conclusions can be drawn.

Ionospheric origin of magnetospheric O+ ions

Flows of thermal atomic oxygen (O+) ions are deduced from topside ionospheric plasma density profiles. The mean flux within most of the polar cap is of the order of 10^12 m^{−2} s^{−1}, a figure which is consistent with both theoretical and experimental estimates of the light ion polar wind at greater altitudes. Larger flows (up to 6 × 10^12 m^{−2} s^{−1}) are observed near the poleward edge of the night-side statistical auroral oval, a feature not reproduced in the light ion flux. The implication is one of a low altitude acceleration mechanism, acting upon the O+ ions at these latitudes and at heights above that at which the fluxes are observed. Such a process would enable ions to escape from the ionosphere because they do not exchange charge with neutral hydrogen. The observations are in general agreement with energetic O+ ions as previously observed in various parts of the magnetosphere.

Basic concepts for convection parameterization in weather forecast and climate models: COST Action ES0905 final report

The research network “Basic Concepts for Convection Parameterization in Weather Forecast and Climate Models” was organized with European funding (COST Action ES0905) for the period of 2010–2014. Its extensive brainstorming suggests how the subgrid-scale parameterization problem in atmospheric modeling, especially for convection, can be examined and developed from the point of view of a robust theoretical basis. Our main cautions are current emphasis on massive observational data analyses and process studies. The closure and the entrainment–detrainment problems are identified as the two highest priorities for convection parameterization under the mass–flux formulation. The need for a drastic change of the current European research culture as concerns policies and funding in order not to further deplete the visions of the European researchers focusing on those basic issues is emphasized.

Observational and energetics constraints on the non-conservation of potential/Conservative Temperature and implications for ocean modelling

This paper seeks to elucidate the fundamental differences between the nonconservation of potential temperature and that of Conservative Temperature, in order to better understand the relative merits of each quantity for use as the heat variable in numerical ocean models. The main result is that potential temperature is found to behave similarly to entropy, in the sense that its nonconservation primarily reflects production/destruction by surface heat and freshwater fluxes; in contrast, the nonconservation of Conservative Temperature is found to reflect primarily the overall compressible work of expansion/contraction. This paper then shows how this can be exploited to constrain the nonconservation of potential temperature and entropy from observed surface heat fluxes, and the nonconservation of Conservative Temperature from published estimates of the mechanical energy budgets of ocean numerical models. Finally, the paper shows how to modify the evolution equation for potential temperature so that it is exactly equivalent to using an exactly conservative evolution equation for Conservative Temperature, as was recently recommended by IOC et al. (2010). This result should in principle allow ocean modellers to test the equivalence between the two formulations, and to indirectly investigate to what extent the budget of derived nonconservative quantities such as buoyancy and entropy can be expected to be accurately represented in ocean models.

Sensory profiles and consumer acceptability of a range of sugar-reduced products on the UK market

Current UK intake of non-milk extrinsic sugars (NMES) is above recommendations. Reducing the sugar content of processed high sugar foods through reformulation is one option for reducing consumption of NMES at a population level. However, reformulation can alter the sensory attributes of food products and influence consumer liking. This study evaluated consumer acceptance of a selection of products that are commercially-available in the UK; these included regular and sugar-reduced baked beans, strawberry jam, milk chocolate, cola and cranberry & raspberry juice. Sweeteners were present in the reformulated chocolate (maltitol), cola (aspartame and acesulfame-K) and juice (sucralose) samples. Healthy, non-smoking consumers (n = 116; 55 men, 61 women, age: 33 ± 9 years; BMI: 25.7 ± 4.6 kg/m2) rated the products for overall liking and on liking of appearance, flavor and texture using a nine-point hedonic scale. There were significant differences between standard and reduced sugar products in consumers’ overall liking and on liking of each modality (appearance, flavor and texture; all P < 0.0001). For overall liking, only the regular beans and cola were significantly more liked than their reformulated counterparts (P < 0.0001). Cluster analysis identified three consumer clusters that were representative of different patterns of consumer liking. For the largest cluster (cluster 3: 45%), there was a significant difference in mean liking scores across all products, except jam. Differences in liking were predominantly driven by sweet taste in 2 out of 3 clusters. The current research has demonstrated that a high proportion of consumers prefer conventional products over sugar-reduced products across a wide range of product types (45%) or across selected products (27%), when tasted unbranded, and so there is room for further optimization of commercial reduced sugar products that were evaluated in the current study. Future work should evaluate strategies to facilitate compliance to dietary recommendations on NMES and free sugars, such as the impact of sugar-reduced food exposure on their acceptance.

An evaluation of the theoretical potential and practical opportunity for using greywater for domestic purposes in Ghana

Assessments concerning the effects of climate change, water resource availability and water deprivation in West Africa have not frequently considered the positive contribution to be derived from collecting and reusing water for domestic purposes. Where the originating water is taken from a clean water source and has been used the first time for washing or bathing, this water is commonly called “greywater”. Greywater is a prolific resource that is generated wherever people live. Treated greywater can be used for domestic cleaning, for flushing toilets where appropriate, for washing cars, sometimes for watering kitchen gardens, and for clothes washing prior to rinsing. Therefore, a large theoretical potential exists to increase total water resource availability if greywater were to be widely reused. Locally treated greywater reduces the distribution network requirement, lower construction effort and cost and, wherever possible, minimising the associated carbon footprint. Such locally treated greywater offers significant practical opportunities for increasing the total available water resources at a local level. The reuse of treated greywater is one important action that will help to mitigate the reducing availability of clean water supplies in some areas, and the expected mitigation required in future aligns well with WHO/UNICEF (2012) aspirations. The evaluation of potential opportunities for prioritising greywater systems to support water reuse takes into account the availability of water resources, water use indicators and published estimates in order to understand typical patterns of water demand. The approach supports knowledge acquisition regarding local conditions for enabling capacity building for greywater reuse, the understanding of systems that are most likely to encourage greywater reuse, and practices and future actions to stimulate greywater infrastructure planning, design and implementation. Although reuse might be considered to increase the uncertainty of achieving a specified quality of the water supply, robust methods and technologies are available for local treatment. Resource strategies for greywater reuse have the potential to consistently improve water efficiency and availability in water impoverished and water stressed regions of Ghana and West Africa. Untreated greywater is referred to as “greywater”; treated greywater is referred to as “treated greywater” in this paper.

A critical evaluation of the ability of the Spinning Enhanced Visible and Infrared Imager (SEVIRI) thermal infrared red-green-blue rendering to identify dust events: theoretical analysis

Using a combination of idealized radiative transfer simulations and a case study from the first field campaign of the Saharan Mineral Dust Experiment (SAMUM) in southern Morocco, this paper provides a systematic assessment of the limitations of the widely used Spinning Enhanced Visible and Infrared Imager (SEVIRI) red-green-blue (RGB) thermal infrared dust product. Both analyses indicate that the ability of the product to identify dust, via its characteristic pink coloring, is strongly dependent on the column water vapor, the lower tropospheric lapse rate, and dust altitude. In particular, when column water vapor exceeds ∼20–25 mm, dust presence, even for visible optical depths of the order 0.8, is effectively masked. Variability in dust optical properties also has a marked impact on the imagery, primarily as a result of variability in dust composition. There is a moderate sensitivity to the satellite viewing geometry, particularly in moist conditions. The underlying surface can act to confound the signal seen through variations in spectral emissivity, which are predominantly manifested in the 8.7μm SEVIRI channel. In addition, if a temperature inversion is present, typical of early morning conditions over the Sahara and Sahel, an increased dust loading can actually reduce the pink coloring of the RGB image compared to pristine conditions. Attempts to match specific SEVIRI observations to simulations using SAMUM measurements are challenging because of high uncertainties in surface skin temperature and emissivity. Recommendations concerning the use and interpretation of the SEVIRI RGB imagery are provided on the basis of these findings.

Easterly wave disturbances over Northeast Brazil: an observational analysis

This paper aims to identify the circulation associated with Easterly Wave Disturbances (EWDs) that propagate toward the Eastern Northeast Brazil (ENEB) and their impact on the rainfall over ENEB during 2006 and 2007 rainy seasons (April–July). The EWDs identification and trajectory are analyzed using an automatic tracking technique (TracKH). The EWDs circulation patterns and their main features were obtained using the composite technique. To evaluate the TracKH efficiency, a validation was done by comparing the EWDs number tracked against observed cases obtained from an observational analysis. The mean characteristics of EWDs are 5.5-day period, propagation speed of ~9.5 m·s−1, and a 4500 km wavelength. A synoptic analysis shows that between days −2 d and 0 d, the low level winds presented cyclonic relative vorticity and convergence anomalies both in 2006 and 2007. The EWDs signals are strongest at low levels. The EWDs propagation is associated with relative humidity and precipitation positive anomalies and OLR and omega negative anomalies. The EWDs tracks are seen over all ENEB and their lysis occurs between the ENEB and marginally inside the continent. The tracking captured 71% of EWDs in all periods, indicating that an objective analysis is a promising method for EWDs detection.