Contribution of the double layer to transient faradaic processes: implications for hydrodynamic modulated voltammetry of nanostructures

The electrochemistry of Pt nanostructured electrodes is investigated using hydrodynamic modulated voltammetry (HMV). Here a liquid crystal templating process is used to produce platinum-modified electrodes with a range of surface areas (roughness factor 42.4-280.8). The electroreduction of molecular oxygen at these nanostructured platinum surfaces is used to demonstrate the ability of HMV to discriminate between faradaic and nonfaradaic electrode reactions. The HMV approach shows that the reduction of molecular oxygen experiences considerable signal loss within the high pseudocapacitive region of the voltammetry. Evidence for the contribution of the double layer to transient mass transfer events is presented. In addition, a model circuit and appropriate theoretical analysis are used to illustrate the transient responses of a time variant faradaic component. This in conjunction with the experimental evidence shows that, far from being a passive component in this system, the double layer can contribute to HMV faradaic reactions under certain conditions.

A supramolecular polymer based on tweezer-type pi-pi stacking interactions: molecular design for healability and enhanced toughness

An elastomeric, healable, supramolecular polymer blend comprising a chain-folding polyimide and a telechelic polyurethane with pyrenyl end groups is compatibilized by aromatic pi-pi stacking between the pi-electron-deficient diimide groups and the pi-electron-rich pyrenyl units. This interpolymer interaction is the key to forming a tough, healable, elastomeric material. Variable-temperature FTIR analysis of the bulk material also conclusively demonstrates the presence of hydrogen bonding, which complements the pi-pi stacking interactions. Variable-temperature SAXS analysis shows that the healable polymeric blend has a nanophase-separated morphology and that the X-ray contrast between the two types of domain increases with increasing temperature, a feature that is repeatable over several heating and cooling cycles. A fractured sample of this material reproducibly regains more than 95% of the tensile modulus, 91% of the elongation to break, and 77% of the modulus of toughness of the pristine material.

Estimating climatically relevant singular vectors for decadal predictions of the Atlantic Ocean

A key aspect in designing an ecient decadal prediction system is ensuring that the uncertainty in the ocean initial conditions is sampled optimally. Here, we consider one strategy to address this issue by investigating the growth of optimal perturbations in the HadCM3 global climate model (GCM). More specically, climatically relevant singular vectors (CSVs) - the small perturbations which grow most rapidly for a specic initial condition - are estimated for decadal timescales in the Atlantic Ocean. It is found that reliable CSVs can be estimated by running a large ensemble of integrations of the GCM. Amplication of the optimal perturbations occurs for more than 10 years, and possibly up to 40 years. The identi ed regions for growing perturbations are found to be in the far North Atlantic, and these perturbations cause amplication through an anomalous meridional overturning circulation response. Additionally, this type of analysis potentially informs the design of future ocean observing systems by identifying the sensitive regions where small uncertainties in the ocean state can grow maximally. Although these CSVs are expensive to compute, we identify ways in which the process could be made more ecient in the future.

Design and development of a haptic dental training system - hapTEL

This paper presents a novel design of a virtual dental training system (hapTEL) using haptic technology. The system allows dental students to learn and practice procedures such as dental drilling, caries removal and cavity preparation for tooth restoration. This paper focuses on the hardware design, development and evaluation aspects in relation to the dental training and educational requirements. Detailed discussions on how the system offers dental students a natural operational position are documented. An innovative design of measuring and connecting the dental tools to the haptic device is also shown. Evaluation of the impact on teaching and learning is discussed.

Changes of interannual NAO variability in response to greenhouse gases forcing

Observations show that there was change in interannual North Atlantic Oscillation (NAO) variability in the mid-1970s. This change was characterized by an eastward shift of the NAO action centres, a poleward shift of zonal wind anomalies and a downstream extension of climate anomalies associated with the NAO. The NAO interannual variability for the period after the mid-1970s has an annular mode structure that penetrates deeply into the stratosphere, indicating a strengthened relationship between the NAO and the Arctic Oscillation (AO) and strengthened stratosphere-troposphere coupling. In this study we have investigated possible causes of these changes in the NAO by carrying out experiments with an atmospheric GCM. The model is forced either by doubling CO2, or increasing sea surface temperatures (SST), or both. In the case of SST forcing the SST anomaly is derived from a coupled model simulation forced by increasing CO2. Results indicate that SST and CO2 change both force a poleward and eastward shift in the pattern of interannual NAO variability and the associated poleward shift of zonal wind anomalies, similar to the observations. The effect of SST change can be understood in terms of mean changes in the troposphere. The direct effect of CO2 change, in contrast, can not be understood in terms of mean changes in the troposphere. However, there is a significant response in the stratosphere, characterized by a strengthened climatological polar vortex with strongly enhanced interannual variability. In this case, the NAO interannual variability has a strong link with the variability over the North Pacific, as in the annular AO pattern, and is also strongly related to the stratospheric vortex, indicating strengthened stratosphere-troposphere coupling. The similarity of changes in many characteristics of NAO interannual variability between the model response to doubling CO2 and those in observations in the mid-1970s implies that the increase of greenhouse gas concentration in the atmosphere, and the resulting changes in the stratosphere, might have played an important role in the multidecadal change of interannual NAO variability and its associated climate anomalies during the late twentieth century. The weak change in mean westerlies in the troposphere in response to CO2 change implies that enhanced and eastward extended mid-latitude westerlies in the troposphere might not be a necessary condition for the poleward and eastward shift of the NAO action centres in the mid-1970s.

Case studies in interannual to decadal climate predictability

The predictability of ocean and climate variables is investigated, using a perfect model-based case study approach that recognises that predictability is dependent on the initial climate state. In line with previous studies, large scale ocean variables, show predictability for several years or more; by contrast, the predictability of climate variables is generally limited to, 2 years at most. That predictability shows high sensitivity to the initial state is demonstrated by predictable climate signals, arising in different regions, variables and seasons for different initial conditions. The predictability of climate variables, in the second year is of particular interest, because this is beyond the timescale that is usually considered to be the limit, of seasonal predictability. For different initial conditions, second year predictability is found in: temperatures in southeastern, North America (winter) and western Europe (winter and summer), and precipitation in India (summer monsoon) and in the tropical, South Atlantic. Second year predictability arises either from persistence of large-scale sea surface temperature (SST) and, related ocean heat content anomalies, particularly in regions such as the North Atlantic and Southern Ocean, or from mechanisms, that involve El Nino Southern Oscillation (ENSO) dynamics.

Sarah Kane: Cool Britannia's reluctant feminist

Aleks Sierz in his important survey of mid 1990s drama has identified the plays of Sarah Kane as exemplars of what he terms ‘In-Yer Face’ theatre. Sierz argues that Kane and her contemporaries such as Mark Ravenhill and Judy Upton represent a break with the ideological concerns of the previous generation of playwrights such as Doug Lucie and Stephen Lowe, whose work was shaped through recognizable political concerns, often in direct opposition to Thatcherism. In contrast Sarah Kane and her generation have frequently been seen as literary embodiments of ‘Thatcher’s Children’, whereby following the fall of the Berlin Wall and the inertia of the Major years, their drama eschews a recognizable political position, and seems more preoccupied with the plight of individuals cut adrift from society. In the case of Sarah Kane her frequently quoted statement, ‘I have no responsibility as a woman writer because I don’t believe there’s such a thing’, has compounded this perception. Moreover, its dogmatism also echoes the infamous comments attributed to Mrs Thatcher regarding the role of the individual to society. However, this article seeks to reassess Kane’s position as a woman writer and will argue that her drama is positioned somewhere between the female playwrights who emerged after 1979 such as Sarah Daniels, Timberlake Wertenbaker and Clare McIntyre, whose drama was distinguished by overtly feminist concerns, and its subsequent breakdown, best exemplified by the brief cultural moment associated with the newly elected Blair government known as ‘Cool Britannia’. Drawing on a variety of sources, including Kane’s unpublished monologues, written while she was a student just after Mrs Thatcher left office, this paper will argue that far from being an exponent of post-feminism, Kane’s drama frequently revisits and is influenced by the generation of dramatists whose work was forged out the sharp ideological positions that characterized the 1980s and a direct consequence of Thatcherism.

A review of climate risk information for adaptation and development planning

Although the use of climate scenarios for impact assessment has grown steadily since the 1990s, uptake of such information for adaptation is lagging by nearly a decade in terms of scientific output. Nonetheless, integration of climate risk information in development planning is now a priority for donor agencies because of the need to prepare for climate change impacts across different sectors and countries. This urgency stems from concerns that progress made against Millennium Development Goals (MDGs) could be threatened by anthropogenic climate change beyond 2015. Up to this time the human signal, though detectable and growing, will be a relatively small component of climate variability and change. This implies the need for a twin-track approach: on the one hand, vulnerability assessments of social and economic strategies for coping with present climate extremes and variability, and, on the other hand, development of climate forecast tools and scenarios to evaluate sector-specific, incremental changes in risk over the next few decades. This review starts by describing the climate outlook for the next couple of decades and the implications for adaptation assessments. We then review ways in which climate risk information is already being used in adaptation assessments and evaluate the strengths and weaknesses of three groups of techniques. Next we identify knowledge gaps and opportunities for improving the production and uptake of climate risk information for the 2020s. We assert that climate change scenarios can meet some, but not all, of the needs of adaptation planning. Even then, the choice of scenario technique must be matched to the intended application, taking into account local constraints of time, resources, human capacity and supporting infrastructure. We also show that much greater attention should be given to improving and critiquing models used for climate impact assessment, as standard practice. Finally, we highlight the over-arching need for the scientific community to provide more information and guidance on adapting to the risks of climate variability and change over nearer time horizons (i.e. the 2020s). Although the focus of the review is on information provision and uptake in developing regions, it is clear that many developed countries are facing the same challenges. Copyright © 2009 Royal Meteorological Society

Processes governing the predictability of the Atlantic meridional overturning circulation in a coupled GCM

The processes that govern the predictability of decadal variations in the North Atlantic meridional overturning circulation (MOC) are investigated in a long control simulation of the ECHO-G coupled atmosphere–ocean model. We elucidate the roles of local stochastic forcing by the atmosphere, and other potential ocean processes, and use our results to build a predictive regression model. The primary influence on MOC variability is found to come from air–sea heat fluxes over the Eastern Labrador Sea. The maximum correlation between such anomalies and the variations in the MOC occurs at a lead time of 2 years, but we demonstrate that the MOC integrates the heat flux variations over a period of 10 years. The corresponding univariate regression model accounts for 74.5% of the interannual variability in the MOC (after the Ekman component has been removed). Dense anomalies to the south of the Greenland-Scotland ridge are also shown to precede the overturning variations by 4–6 years, and provide a second predictor. With the inclusion of this second predictor the resulting regression model explains 82.8% of the total variance of the MOC. This final bivariate model is also tested during large rapid decadal overturning events. The sign of the rapid change is always well represented by the bivariate model, but the magnitude is usually underestimated, suggesting that other processes are also important for these large rapid decadal changes in the MOC.

Evaluating the potential for statistical decadal predictions of sea surface temperatures with a perfect model approach

We explore the potential for making statistical decadal predictions of sea surface temperatures (SSTs) in a perfect model analysis, with a focus on the Atlantic basin. Various statistical methods (Lagged correlations, Linear Inverse Modelling and Constructed Analogue) are found to have significant skill in predicting the internal variability of Atlantic SSTs for up to a decade ahead in control integrations of two different global climate models (GCMs), namely HadCM3 and HadGEM1. Statistical methods which consider non-local information tend to perform best, but which is the most successful statistical method depends on the region considered, GCM data used and prediction lead time. However, the Constructed Analogue method tends to have the highest skill at longer lead times. Importantly, the regions of greatest prediction skill can be very different to regions identified as potentially predictable from variance explained arguments. This finding suggests that significant local decadal variability is not necessarily a prerequisite for skillful decadal predictions, and that the statistical methods are capturing some of the dynamics of low-frequency SST evolution. In particular, using data from HadGEM1, significant skill at lead times of 6–10 years is found in the tropical North Atlantic, a region with relatively little decadal variability compared to interannual variability. This skill appears to come from reconstructing the SSTs in the far north Atlantic, suggesting that the more northern latitudes are optimal for SST observations to improve predictions. We additionally explore whether adding sub-surface temperature data improves these decadal statistical predictions, and find that, again, it depends on the region, prediction lead time and GCM data used. Overall, we argue that the estimated prediction skill motivates the further development of statistical decadal predictions of SSTs as a benchmark for current and future GCM-based decadal climate predictions.

Examination of long-wave radiative bias in general circulation models over North Africa during May–July

Satellite data are used to quantify and examine the bias in the outgoing long-wave (LW) radiation over North Africa during May–July simulated by a range of climate models and the Met Office global numerical weather prediction (NWP) model. Simulations from an ensemble-mean of multiple climate models overestimate outgoing clear-sky long-wave radiation (LWc) by more than 20 W m−2 relative to observations from Clouds and the Earth's Radiant Energy System (CERES) for May–July 2000 over parts of the west Sahara, and by 9 W m−2 for the North Africa region (20°W–30°E, 10–40°N). Experiments with the atmosphere-only version of the High-resolution Hadley Centre Global Environment Model (HiGEM), suggest that including mineral dust radiative effects removes this bias. Furthermore, only by reducing surface temperature and emissivity by unrealistic amounts is it possible to explain the magnitude of the bias. Comparing simulations from the Met Office NWP model with satellite observations from Geostationary Earth Radiation Budget (GERB) instruments suggests that the model overestimates the LW by 20–40 W m−2 during North African summer. The bias declines over the period 2003–2008, although this is likely to relate to improvements in the model and inhomogeneity in the satellite time series. The bias in LWc coincides with high aerosol dust loading estimated from the Ozone Monitoring Instrument (OMI), including during the GERBILS field campaign (18–28 June 2007) where model overestimates in LWc greater than 20 W m−2 and OMI-estimated aerosol optical depth (AOD) greater than 0.8 are concurrent around 20°N, 0–20°W. A model-minus-GERB LW bias of around 30 W m−2 coincides with high AOD during the period 18–21 June 2007, although differences in cloud cover also impact the model–GERB differences. Copyright © Royal Meteorological Society and Crown Copyright, 2010