RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297tochromism of the intense (ε ≈ 104 M–1cm–1) charge-transfer absorption band in the visible region and by DFT calculations. Oxidation of the compounds occurs mainly at the R-DAB·– radical ligand to produce UV/Vis/NIR and electron paramagnetic resonance (EPR) spectroelectrochemically detectable RuIII species, whereas the reduction proceeds less reversibly and yields predominantly (R-DAB)-ligand-based spin for the 4-methoxyphenyl derivative, measured at low temperature. The results are discussed with respect to metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.

The role of evaporating showers in the transfer of sting-jet momentum to the surface

The most damaging winds in a severe extratropical cyclone often occur just ahead of the evaporating ends of cloud filaments emanating from the so-called cloud head. These winds are associated with low-level jets (LLJs), sometimes occurring just above the boundary layer. The question then arises as to how the high momentum is transferred to the surface. An opportunity to address this question arose when the severe ‘St Jude's Day’ windstorm travelled across southern England on 28 October 2013. We have carried out a mesoanalysis of a network of 1 min resolution automatic weather stations and high-resolution Doppler radar scans from the sensitive S-band Chilbolton Advanced Meteorological Radar (CAMRa), along with satellite and radar network imagery and numerical weather prediction products. We show that, although the damaging winds occurred in a relatively dry region of the cyclone, there was evidence within the LLJ of abundant precipitation residues from shallow convective clouds that were evaporating in a localized region of descent. We find that pockets of high momentum were transported towards the surface by the few remaining actively precipitating convective clouds within the LLJ and also by precipitation-free convection in the boundary layer that was able to entrain evaporatively cooled air from the LLJ. The boundary-layer convection was organized in along-wind rolls separated by 500 to about 3000 m, the spacing varying according to the vertical extent of the convection. The spacing was greatest where the strongest winds penetrated to the surface. A run with a medium-resolution version of the Weather Research and Forecasting (WRF) model was able to reproduce the properties of the observed LLJ. It confirmed the LLJ to be a sting jet, which descended over the leading edge of a weaker cold-conveyor-belt jet.

Food-chain transfer of zinc from contaminated Urtica dioica and Acer pseudoplatanus L. to Microlophium carnosum and Drepanosiphum platanoidis Schrank

This study examines the food-chain transfer of Zn from two plant species, Urtica dioica (stinging nettle) and Acer pseudoplatanus (sycamore maple), into their corresponding aphid species, Microlophium carnosum and Drepanosiphum platanoidis. The plants were grown in a hydroponic system using solutions with increasing concentrations of Zn from 0.02 to 41.9 mg Zn/l. Above-ground tissue concentrations in U. dioica and M. carnosum increased with increasing Zn exposure (p < 0.001). Zn concentrations in A. pseudoplatanus also increased with solution concentration from the control to the 9.8 mg Zn/l solution, above which concentrations remained constant. Zn concentrations in both D. platanoidis and the phloem tissue of A. pseudoplatanus were not affected by the Zn concentration in the watering solution. It appears that A. pseudoplatanus was able to limit Zn transport in the phloem, resulting in constant Zn exposure to the aphids. Zn concentrations in D. platanoidis were around three times those in M. carnosum. Concentrations of Zn in two aphid species are dependant on species and exposure.

On the climate response of the low-latitude Pacific Ocean to changes in the global freshwater cycle

Under global warming, the predicted intensification of the global freshwater cycle will modify the net freshwater flux at the ocean surface. Since the freshwater flux maintains ocean salinity structures, changes to the density-driven ocean circulation are likely. A modified ocean circulation could further alter the climate, potentially allowing rapid changes, as seen in the past. The relevant feedback mechanisms and timescales are poorly understood in detail, however, especially at low latitudes where the effects of salinity are relatively subtle. In an attempt to resolve some of these outstanding issues, we present an investigation of the climate response of the low-latitude Pacific region to changes in freshwater forcing. Initiated from the present-day thermohaline structure, a control run of a coupled ocean-atmosphere general circulation model is compared with a perturbation run in which the net freshwater flux is prescribed to be zero over the ocean. Such an extreme experiment helps to elucidate the general adjustment mechanisms and their timescales. The atmospheric greenhouse gas concentrations are held constant, and we restrict our attention to the adjustment of the upper 1,000 m of the Pacific Ocean between 40°N and 40°S, over 100 years. In the perturbation run, changes to the surface buoyancy, near-surface vertical mixing and mixed-layer depth are established within 1 year. Subsequently, relative to the control run, the surface of the low-latitude Pacific Ocean in the perturbation run warms by an average of 0.6°C, and the interior cools by up to 1.1°C, after a few decades. This vertical re-arrangement of the ocean heat content is shown to be achieved by a gradual shutdown of the heat flux due to isopycnal (i.e. along surfaces of constant density) mixing, the vertical component of which is downwards at low latitudes. This heat transfer depends crucially upon the existence of density-compensating temperature and salinity gradients on isopycnal surfaces. The timescale of the thermal changes in the perturbation run is therefore set by the timescale for the decay of isopycnal salinity gradients in response to the eliminated freshwater forcing, which we demonstrate to be around 10-20 years. Such isopycnal heat flux changes may play a role in the response of the low-latitude climate to a future accelerated freshwater cycle. Specifically, the mechanism appears to represent a weak negative sea surface temperature feedback, which we speculate might partially shield from view the anthropogenically-forced global warming signal at low latitudes. Furthermore, since the surface freshwater flux is shown to play a role in determining the ocean's thermal structure, it follows that evaporation and/or precipitation biases in general circulation models are likely to cause sea surface temperature biases.

Food-chain transfer of cadmium and zinc from contaminated Urtica dioica to Helix aspersa and Lumbricus terrestris

The present study examines the potential of Urtica dioica as an ecologically relevant species for use in ecotoxicological testing. It is prevalent in degraded ecosystems and is a food source for invertebrates. Urtica dioica grown in hydroponic solutions containing from less than 0.003 to 5.7 mg Cd/L or from 0.02 to 41.9 mg Zn/L accumulated metals resulting in leaf tissue concentrations in the range of 0.10 to 24.9 mg Cd/kg or 22.5 to 2,772.0 mg Zn/kg. No toxicological effects were apparent except at the highest concentrations tested, suggesting that this species may be an important pathway for transfer of metals to primary plant consumers. Helix aspersa and Lumbricus terrestris were fed the Cd- and Zn-rich leaves of U. dioica for six and four weeks, respectively. Cadmium and Zn body load increased with increasing metal concentration in the leaves (p < 0.001). Ratios of invertebrate metal concentration to leaf metal concentration were in the range of 1:0.03 to 1:1.4 for Cd and 1:0.2 to 1:2.8 for Zn in H. aspersa and 1:0.002 to 1:3.9 for Cd and 1:0.2 to 1:8.8 for Zn in L. terrestris. Helix aspersa Cd and Zn tissue concentrations (15.5 and 1,220.2 mg/kg, respectively) were approximately threefold those in L. terrestris when both species were fed nettle leaves with concentrations of approximately 23 mg Cd/ kg and 3,400 mg Zn/kg. Models demonstrate that L. terrestris Cd tissue concentrations (r(2) = 0.74, p < 0.001) and H. aspersa Zn tissue concentrations (r(2) = 0.69, p < 0.001) can be estimated from concentrations of Cd and Zn within the leaves of U. dioica and suggest that reasonably reproducible results can be obtained using these species for ecotoxicological testing.

Evaluation of two hybrid metric-conceptual models, for simulating phosphorus transfer from agricultural land in the river enborne, a lowland UK catchment

Across Europe, elevated phosphorus (P) concentrations in lowland rivers have made them particularly susceptible to eutrophication. This is compounded in southern and central UK by increasing pressures on water resources, which may be further enhanced by the potential effects of climate change. The EU Water Framework Directive requires an integrated approach to water resources management at the catchment scale and highlights the need for modelling tools that can distinguish relative contributions from multiple nutrient sources and are consistent with the information content of the available data. Two such models are introduced and evaluated within a stochastic framework using daily flow and total phosphorus concentrations recorded in a clay catchment typical of many areas of the lowland UK. Both models disaggregate empirical annual load estimates, derived from land use data, as a function of surface/near surface runoff, generated using a simple conceptual rainfall-runoff model. Estimates of the daily load from agricultural land, together with those from baseflow and point sources, feed into an in-stream routing algorithm. The first model assumes constant concentrations in runoff via surface/near surface pathways and incorporates an additional P store in the river-bed sediments, depleted above a critical discharge, to explicitly simulate resuspension. The second model, which is simpler, simulates P concentrations as a function of surface/near surface runoff, thus emphasising the influence of non-point source loads during flow peaks and mixing of baseflow and point sources during low flows. The temporal consistency of parameter estimates and thus the suitability of each approach is assessed dynamically following a new approach based on Monte-Carlo analysis. (c) 2004 Elsevier B.V. All rights reserved.

Transfer of members of the genus Falcivibrio to the genus Mobiluncus, and emended description of the genus Mobiluncus

It has long been thought that the genera Mobiluncus and Falcivibrio contain the same organisms. Using a polyphasic approach, it was found that Mobiluncus curtisii and Mobiluncus mulieris were the same as Falcivibrio vaginalis and Falcivibrio grandis, respectively. As the genus name Mobiluncus takes precedence, it is proposed that F. vaginalis and F. grandis be transferred to the genus Mobiluncus. In agreement with previous studies, results from phenotypic tests did not support the separation of M. curtisii strains into its two subspecies, M. curtisii subsp. curtisii and M. curtisii subsp. holmesii. Phenotypic complexity within M. curtisii dictates that the species should be treated as a complex until more in-depth analyses of the species have been performed. Phylogenetic analyses, based on 16S rRNA gene sequences, demonstrated that the genus Mobiluncus was associated with Varibaculum cambriense and the two subspecies of Actinomyces neuii, and that A. neuii is only distantly related to Actinomyces sensu stricto.

Local environmental action in Japan: the transfer of the groundwork approach

This paper is the basis for a report on the transfer of the UK Groundwork approach to Japan. It details the background and history of Groundwork in the UK and sets out some of the relevant context in Japan. A Japanese case study (plus two further secondary cases) is detailed and conclusions and recommendations are drawn from the work to help suggest future directions for GW and environmental action in Japan in the future.

In search of the aim of the free movement of persons provisions: has the Court of Justice missed the point?

The Court of Justice has, over the years, often been vilified for exceeding the limits of its jurisdiction by interpreting the provisions of Community legislation in a way not seem originally envisaged by its drafters. A recent example of this approach was a cluster of cases in the context of the free movement of workers and the freedom of establishment (Ritter-Coulais and its progeny), where the Court included within the scope of those provisions situations which, arguably, did not present a sufficient link with their (economic) aim. In particular, in that case law the Court accepted that the mere exercise of free movement for the purpose of taking up residence in the territory of another Member State whilst continuing to exercise an economic activity in the State of origin, suffices for bringing a Member State national within the scope of Articles 39 and 43 EC. It is argued that the most plausible explanation for this approach is that the Court now wishes to re-read the economic fundamental freedoms in such a way as to include within their scope all economically active Union citizens, irrespective of whether their situation presents a sufficient link with the exercise of an economic activity in a cross-border context. It is suggested that this approach is problematic for a number of reasons. It is, therefore, concluded that the Court should revert to its orthodox approach, according to which only situations that involve Union citizens who have moved between Member States for the purpose of taking up an economic activity should be included within the scope of the market freedoms.

Adeno-associated virus-8-Mediated intravenous transfer of myostatin propeptide leads to systemic functional improvements of slow but not fast muscle

Myostatin is a member of the transformating growth factor-_ (TGF-_) superfamily of proteins and is produced almost exclusively in skeletal muscle tissue, where it is secreted and circulates as a serum protein. Myostatin acts as a negative regulator of muscle mass through the canonical SMAD2/3/4 signaling pathway. Naturally occurring myostatin mutants exhibit a ‘double muscling’ phenotype in which muscle mass is dramatically increased as a result of both hypertrophy and hyperplasia. Myostatin is naturally inhibited by its own propeptide; therefore, we assessed the impact of adeno associated virus-8 (AAV8) myostatin propeptide vectors when systemically introduced in MF-1 mice. We noted a significant systemic increase in muscle mass in both slow and fast muscle phenotypes, with no evidence of hyperplasia; however, the nuclei-to- cytoplasm ratio in all myofiber types was significantly reduced. An increase in muscle mass in slow (soleus) muscle led to an increase in force output; however, an increase in fast (extensor digitorum longus [EDL]) muscle mass did not increase force output. These results suggest that the use of gene therapeutic regimens of myostatin inhibition for age-related or disease-related muscle loss may have muscle-specific effects.

Coordinated Cluster and ground-based instrument observations of transient changes in the magnetopause boundary layer during an interval of predominantly northward IMF: relation to reconnection pulses and FTE signatures

We study a series of transient entries into the low-latitude boundary layer (LLBL) of all four Cluster spacecraft during an outbound pass through the mid-afternoon magnetopause ([X(GSM), Y(GSM), Z(GSM)] approximate to [2, 7, 9] R(E)). The events take place during an interval of northward IMF, as seen in the data from the ACE satellite and lagged by a propagation delay of 75 min that is well-defined by two separate studies: (1) the magnetospheric variations prior to the northward turning (Lockwood et al., 2001, this issue) and (2) the field clock angle seen by Cluster after it had emerged into the magnetosheath (Opgenoorth et al., 2001, this issue). With an additional lag of 16.5 min, the transient LLBL events cor-relate well with swings of the IMF clock angle (in GSM) to near 90degrees. Most of this additional lag is explained by ground-based observations, which reveal signatures of transient reconnection in the pre-noon sector that then take 10-15 min to propagate eastward to 15 MLT, where they are observed by Cluster. The eastward phase speed of these signatures agrees very well with the motion deduced by the cross-correlation of the signatures seen on the four Cluster spacecraft. The evidence that these events are reconnection pulses includes: transient erosion of the noon 630 nm (cusp/cleft) aurora to lower latitudes; transient and travelling enhancements of the flow into the polar cap, imaged by the AMIE technique; and poleward-moving events moving into the polar cap, seen by the EISCAT Svalbard Radar (ESR). A pass of the DMSP-F15 satellite reveals that the open field lines near noon have been opened for some time: the more recently opened field lines were found closer to dusk where the flow transient and the poleward-moving event intersected the satellite pass. The events at Cluster have ion and electron characteristics predicted and observed by Lockwood and Hapgood (1998) for a Flux Transfer Event (FTE), with allowance for magnetospheric ion reflection at Alfvenic disturbances in the magnetopause reconnection layer. Like FTEs, the events are about 1 R(E) in their direction of motion and show a rise in the magnetic field strength, but unlike FTEs, in general, they show no pressure excess in their core and hence, no characteristic bipolar signature in the boundary-normal component. However, most of the events were observed when the magnetic field was southward, i.e. on the edge of the interior magnetic cusp, or when the field was parallel to the magnetic equatorial plane. Only when the satellite begins to emerge from the exterior boundary (when the field was northward), do the events start to show a pressure excess in their core and the consequent bipolar signature. We identify the events as the first observations of FTEs at middle altitudes.

Neurolinguistic measures of typological effects in multilingual transfer: introducing an ERP methodology

This article has two main objectives. First, we offer an introduction to the subfield of generative third language (L3) acquisition. Concerned primarily with modeling initial stages transfer of morphosyntax, one goal of this program is to show how initial stages L3 data make significant contributions toward a better understanding of how the mind represents language and how (cognitive) economy constrains acquisition processes more generally. Our second objective is to argue for and demonstrate how this subfield will benefit from a neuro/psycholinguistic methodological approach, such as event-related potential experiments, to complement the claims currently made on the basis of exclusively behavioral experiments.

Differential uptake, partitioning and transfer of Cd and Zn in the soil-pea plant-aphid system

The biomagnification of trace metals during transfer from contaminated soil to higher trophic levels may potentially result in the exposure of predatory arthropods to toxic concentrations of these elements. This study examined the transfer of Cd and Zn in a soil−plant−arthropod system grown in series of field plots that had received two annual applications of municipal biosolids with elevated levels of Cd and Zn. Results showed that biosolids amendment significantly increased the concentration of Cd in the soil and the shoots of pea plants and the concentration of Zn in the soil, pea roots, shoots, and pods. In addition, the ratio of Cd to Zn concentration showed that Zn was preferentially transferred compared to Cd through all parts of the system. As a consequence, Zn was biomagnified by the system whereas Cd was biominimized. Cd and Zn are considered to exhibit similar behaviors in biological systems. However, the Cd/Zn ratios demonstrated that in this system, Cd is much less labile in the root−shoot−pod and shoot−aphid pathways than Zn.

Transfer of cadmium and zinc from sewage sludge amended soil through a plant–aphid system to newly emerged adult ladybirds (Coccinella septempunctata)

An agricultural soil was amended with sewage sludge at rates equivalent to 0, 10 and 30 t (dry solids) ha−1 and the subsequent transfer of zinc and cadmium through a soil–plant–arthropod system was investigated. Zinc concentration in soil, wheat and aphids increased significantly with sludge amendment rate. Zinc was biomagnified during transfer along the pathway, resulting in concentrations in the aphids four times greater than in the soil. Cadmium concentration in the soil was also significantly elevated by the addition of sludge, but there was no significant difference in cadmium concentration in the shoots of wheat plants. Cadmium concentration in aphids followed the pattern found in plants, but again, differences between treatments were not significant. Aphids collected from the plants were subsequently fed to fourth instar Coccinella septempunctata. Consumption of these aphids did not result in significant differences between treatments in the body burden of newly emerged adult C. septempunctata for either metal. Sequestration of cadmium in the pupal exuviae had a greater effect on the body burden of newly emerged adult ladybirds than for zinc. Results are discussed in relation to possible risks posed by the transfer of trace metals via the soil–plant–arthropod system to predatory arthropods.