Some physical drivers of changes in the winter storm tracks over the North Atlantic and Mediterranean during the Holocene

The winter climate of Europe and the Mediterranean is dominated by the weather systems of the mid-latitude storm tracks. The behaviour of the storm tracks is highly variable, particularly in the eastern North Atlantic, and has a profound impact on the hydroclimate of the Mediterranean region. A deeper understanding of the storm tracks and the factors that drive them is therefore crucial for interpreting past changes in Mediterranean climate and the civilizations it has supported over the last 12 000 years (broadly the Holocene period). This paper presents a discussion of how changes in climate forcing (e.g. orbital variations, greenhouse gases, ice sheet cover) may have impacted on the ‘basic ingredients’ controlling the mid-latitude storm tracks over the North Atlantic and the Mediterranean on intermillennial time scales. Idealized simulations using the HadAM3 atmospheric general circulation model (GCM) are used to explore the basic processes, while a series of timeslice simulations from a similar atmospheric GCM coupled to a thermodynamic slab ocean (HadSM3) are examined to identify the impact these drivers have on the storm track during the Holocene. The results suggest that the North Atlantic storm track has moved northward and strengthened with time since the Early to Mid-Holocene. In contrast, the Mediterranean storm track may have weakened over the same period. It is, however, emphasized that much remains still to be understood about the evolution of the North Atlantic and Mediterranean storm tracks during the Holocene period.

Changes in the Mediterranean climate during the Holocene: insights from global and regional climate modelling

Palaeoproxy records alone are seldom sufficient to provide a full assessment of regional palaeoclimates. To better understand the possible changes in the Mediterranean climate during the Holocene, a series of palaeoclimate integrations for periods spanning the last 12 000 years have been performed and their results diagnosed. These simulations use the HadSM3 global climate model, which is then dynamically downscaled to approximately 50 km using a consistent regional climate model (HadRM3). Changes in the model’s seasonal-mean surface air temperatures and precipitation are discussed at both global and regional scales, along with the physical mechanisms underlying the changes. It is shown that the global model reproduces many of the large-scale features of the mid-Holocene climate (consistent with previous studies) and that the results suggest that many areas within the Mediterranean region were wetter during winter with a stronger seasonal cycle of surface air temperatures during the early Holocene. This precipitation signal in the regional model is strongest in the in the northeast Mediterranean (near Turkey), consistent with low-level wind patterns and earlier palaeosyntheses. It is, however, suggested that further work is required to fully understand the changes in the winter circulation patterns over the Mediterranean region.

Transition metal clusters on graphite

The topic of this work is 3d transition metals deposited on graphite. Spin-polarised density-functional calculations are used to obtain the magnetic moments of deposited adatoms and dimers. Interatomic potentials are also deduced. These are used in molecular dynamics simulations to study cluster formation and to investigate cluster morphology.

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.

Reversible sphere-to-lamellar wetting transition at the interface of a diblock copolymer system

We use ellipsometry to investigate a transition in the morphology of a sphere-forming diblock copolymer thin-film system. At an interface the diblock morphology may differ from the bulk when the interfacial tension favours wetting of the minority domain, thereby inducing a sphere-to-lamella transition. In a small, favourable window in energetics, one may observe this transition simply by adjusting the temperature. Ellipsometry is ideally suited to the study of the transition because the additional interface created by the wetting layer affects the polarisation of light reflected from the sample. Here we study thin films of poly(butadiene-ethylene oxide) (PB-PEO), which order to form PEO minority spheres in a PB matrix. As temperature is varied, the reversible transition from a partially wetting layer of PEO spheres to a full wetting layer at the substrate is investigated.

Effects of polydispersity on the order-disorder transition of diblock copolymer melts

The effect of polydispersity on an AB diblock copolymer melt is investigated using latticebased Monte Carlo simulations. We consider melts of symmetric composition, where the B blocks are monodisperse and the A blocks are polydisperse with a Schultz-Zimm distribution. In agreement with experiment and self-consistent field theory (SCFT), we find that polydispersity causes a significant increase in domain size. It also induces a transition from flat to curved interfaces, with the polydisperse blocks residing on the inside of the interfacial curvature. Most importantly, the simulations show a relatively small shift in the order-disorder transition (ODT) in agreement with experiment, whereas SCFT incorrectly predicts a sizable shift towards higher temperatures.

The transition of the Polish real estate market within a Central and Eastern European context

The real estate market in Poland is a relatively immature market, but one that has been experiencing substantial transformation. The development of the market has been encouraged by a number of factors, including changes arising as a result of new legislation and the migration of capital between capital markets. The progress of the real estate sector towards a western style competitive market has taken place within the gradual transformation of the Polish economy into a free market economy. As investment grade property is in relatively short supply in Poland, investors consider opportunities within the wider CEE block. An analysis of the risk-return characteristics of the three largest CEE real estate markets namely, Poland, Hungary and Czech Republic, shows that the returns in these markets have been negatively correlated with the UK. As these economies and markets evolve, and being part of the wider EU trading block, their economic performance will slowly converge and become more synchronized with their western counterparts. However, the catch-up of the CEE markets to western European performance cycles will be protracted and consequently there are likely to be significant ongoing portfolio risk reduction opportunities