Electrochemical characterisation and anodic stripping voltammetry at mesoporous platinum rotating disc electrodes

Using the technique of liquid crystal templating a rotating disc electrode (RDE) was modified with a high surface area mesoporous platinum film. The surface area of the electrode was characterised by acid voltammetry, and found to be very high (ca. 86 cm(2)). Acid characterisation of the electrode produced distorted voltammograms was interpreted as being due to the extremely large surface area which produced a combination of effects such as localised pH change within the pore environment and also ohmic drop effects. Acid voltammetry in the presence of two different types of surfactant, namely Tween 20 and Triton X-100, suggested antifouling properties associated with the mesoporous deposit. Further analysis of the modified electrode using a redox couple in solution showed typical RDE behaviour although extra capacitive currents were observed due to the large surface area of the electrode. The phenomenon of underpotential deposition was exploited for the purpose of anodic stripping voltammetry and results were compared with data collected for microelectrodes. Underpotential deposition of metal ions at the mesoporous RDE was found to be similar to that at conventional platinum electrodes and mesoporous microelectrodes although the rate of surface coverage was found to be slower at a mesoporous RDE. It was found that a mesoporous RDE forms a suitable system for quantification of silver ions in solution.

Options for support to agriculture and food security under climate change

Agriculture and food security are key sectors for intervention under climate change. Agricultural production is highly vulnerable even to 2C (low-end) predictions for global mean temperatures in 2100, with major implications for rural poverty and for both rural and urban food security. Agriculture also presents untapped opportunities for mitigation, given the large land area under crops and rangeland, and the additional mitigation potential of aquaculture. This paper presents a summary of current knowledge on options to support farmers, particularly smallholder farmers, in achieving food security through agriculture under climate change. Actions towards adaptation fall into two broad overlapping areas: (1) accelerated adaptation to progressive climate change over decadal time scales, for example integrated packages of technology, agronomy and policy options for farmers and food systems, and (2) better management of agricultural risks associated with increasing climate variability and extreme events, for example improved climate information services and safety nets. Maximization of agriculture’s mitigation potential will require investments in technological innovation and agricultural intensification linked to increased efficiency of inputs, and creation of incentives and monitoring systems that are inclusive of smallholder farmers. Food systems faced with climate change need urgent, broad-based action in spite of uncertainties.

A conceptual framework of patient satisfaction with a pharmacy adherence service

Background Patients do not adhere to their medicines for a host of reasons which can include their underlying beliefs as well as the quality of their interactions with healthcare professionals. One way of measuring the outcome of pharmacy adherence services is to assess patient satisfaction but no questionnaire exists that truly captures patients' experiences with these relatively new services. Objective Our objective was to develop a conceptual framework specific to patient satisfaction with a community pharmacy adherence service based on criteria used by patients themselves. Setting The study was based in community pharmacies in one large geographical area of the UK (Surrey). All the work was conducted between October 2008 and September 2010. Methods This study involved qualitative non-participant observation and semi-structured interviewing. We observed the recruitment of patients to the Medicines Use Review (MUR) service and also actual MUR consultations (7). We also interviewed patients (15). Data collection continued until no new themes were identified during analysis. We analysed interviews to firstly create a comprehensive account of themes which had significance within the transcripts, then created sub-themes within super-ordinate categories. We used a structure-process-outcome approach to develop a conceptual framework relating to patient satisfaction with the MUR. Favourable ethical opinion for this study was received from the NHS Surrey Research Ethics Committee on 2nd June 2008. Results Five super-ordinate themes linked to patient satisfaction with the MUR service were identified, including relationships with healthcare providers; attitudes towards healthcare providers; patients' experience of health, healthcare and medicines; patients' views of the MUR service; the logistics of the MUR service. In the conceptual framework, structure was conceptualised as existing relationships, environment, and time; process was conceptualised as related to recruitment and consultation stages; and outcome as two concepts of immediate patient outcomes and satisfaction on reflection. Conclusion We identified and highlighted factors that can influence patient satisfaction with the MUR service and this led to the development of a conceptual framework of patient satisfaction with the MUR service. This can form the basis for developing a questionnaire for measuring patient satisfaction with this and similar pharmacy adherence services. Impact of findings on practice * Pharmacists and researchers can access the relevant ideas presented here in relation to patient satisfaction with pharmacy adherence services. * Researcher can use the conceptual framework as a basis for measuring the quality of pharmacy adherence services. * Community pharmacists can improve the quality of healthcare they provide by realizing concepts relevant to patient satisfaction with adherence services.

Design and optimisation of a large-area process-based model for annual crops

The formulation of a new process-based crop model, the general large-area model (GLAM) for annual crops is presented. The model has been designed to operate on spatial scales commensurate with those of global and regional climate models. It aims to simulate the impact of climate on crop yield. Procedures for model parameter determination and optimisation are described, and demonstrated for the prediction of groundnut (i.e. peanut; Arachis hypogaea L.) yields across India for the period 1966-1989. Optimal parameters (e.g. extinction coefficient, transpiration efficiency, rate of change of harvest index) were stable over space and time, provided the estimate of the yield technology trend was based on the full 24-year period. The model has two location-specific parameters, the planting date, and the yield gap parameter. The latter varies spatially and is determined by calibration. The optimal value varies slightly when different input data are used. The model was tested using a historical data set on a 2.5degrees x 2.5degrees grid to simulate yields. Three sites are examined in detail-grid cells from Gujarat in the west, Andhra Pradesh towards the south, and Uttar Pradesh in the north. Agreement between observed and modelled yield was variable, with correlation coefficients of 0.74, 0.42 and 0, respectively. Skill was highest where the climate signal was greatest, and correlations were comparable to or greater than correlations with seasonal mean rainfall. Yields from all 35 cells were aggregated to simulate all-India yield. The correlation coefficient between observed and simulated yields was 0.76, and the root mean square error was 8.4% of the mean yield. The model can be easily extended to any annual crop for the investigation of the impacts of climate variability (or change) on crop yield over large areas. (C) 2004 Elsevier B.V. All rights reserved.

Simulating the impacts of global warming on wheat in China using a large area crop model

Temperature is one of the most prominent environmental factors that determine plant growth, devel- opment, and yield. Cool and moist conditions are most favorable for wheat. Wheat is likely to be highly vulnerable to further warming because currently the temperature is already close to or above optimum. In this study, the impacts of warming and extreme high temperature stress on wheat yield over China were investigated by using the general large area model (GLAM) for annual crops. The results showed that each 1±C rise in daily mean temperature would reduce the average wheat yield in China by about 4.6%{5.7% mainly due to the shorter growth duration, except for a small increase in yield at some grid cells. When the maximum temperature exceeded 30.5±C, the simulated grain-set fraction declined from 1 at 30.5±C to close to 0 at about 36±C. When the total grain-set was lower than the critical fractional grain-set (0.575{0.6), harvest index and potential grain yield were reduced. In order to reduce the negative impacts of warming, it is crucial to take serious actions to adapt to the climate change, for example, by shifting sowing date, adjusting crop distribution and structure, breeding heat-resistant varieties, and improving the monitoring, forecasting, and early warning of extreme climate events.

Wild bird feeding in a large UK urban area: characteristics and estimates of energy input and individuals supported

Wild bird feeding is popular in domestic gardens across the world. Nevertheless, there is surprisingly little empirical information on certain aspects of the activity and no year-round quantitative records of the amounts and nature of the different foods provided in individual gardens. We sought to characterise garden bird feeding in a large UK urban area in two ways. First, we conducted face-to-face questionnaires with a representative cross-section of residents. Just over half fed birds, the majority doing so year round and at least weekly. Second, a two-year study recorded all foodstuffs put out by households on every provisioning occasion. A median of 628 kcal/garden/day was given. Provisioning level was not significantly influenced by weather or season. Comparisons between the data sets revealed significantly less frequent feeding amongst these ‘keen’ feeders than the face-to-face questionnaire respondents, suggesting that one-off questionnaires may overestimate provisioning frequency. Assuming 100% uptake, the median provisioning level equates to sufficient supplementary resources across the UK to support 196 million individuals of a hypothetical average garden-feeding bird species (based on 10 common UK garden-feeding birds’ energy requirements). Taking the lowest provisioning level recorded (101 kcal/day) as a conservative measure, 31 million of these average individuals could theoretically be supported.

Infrared and millimetre-wave scintillometry in the suburban environment – Part 2: Large-area sensible and latent heat fluxes

A millimetre-wave scintillometer was paired with an infrared scintillometer, enabling estimation of large-area evapotranspiration across northern Swindon, a suburban area in the UK. Both sensible and latent heat fluxes can be obtained using this "two-wavelength" technique, as it is able to provide both temperature and humidity structure parameters, offering a major advantage over conventional single-wavelength scintillometry. The first paper of this two-part series presented the measurement theory and structure parameters. In this second paper, heat fluxes are obtained and analysed. These fluxes, estimated using two-wavelength scintillometry over an urban area, are the first of their kind. Source area modelling suggests the scintillometric fluxes are representative of 5–10 km2. For comparison, local-scale (0.05–0.5 km2) fluxes were measured by an eddy covariance station. Similar responses to seasonal changes are evident at the different scales but the energy partitioning varies between source areas. The response to moisture availability is explored using data from 2 consecutive years with contrasting rainfall patterns (2011–2012). This extensive data set offers insight into urban surface-atmosphere interactions and demonstrates the potential for two-wavelength scintillometry to deliver fluxes over mixed land cover, typically representative of an area 1–2 orders of magnitude greater than for eddy covariance measurements. Fluxes at this scale are extremely valuable for hydro-meteorological model evaluation and assessment of satellite data products

Data assimilation for a coastal area morphodynamic model: Morecambe Bay

This paper investigates the use of data assimilation in coastal area morphodynamic modelling using Morecambe Bay as a study site. A simple model of the bay has been enhanced with a data assimilation scheme to better predict large-scale changes in bathymetry observed in the bay over a 3-year period. The 2DH decoupled morphodynamic model developed for the work is described, as is the optimal interpolation scheme used to assimilate waterline observations into the model run. Each waterline was acquired from a SAR satellite image and is essentially a contour of the bathymetry at some level within the inter-tidal zone of the bay. For model parameters calibrated against validation observations, model performance is good, even without data assimilation. However the use of data assimilation successfully compensates for a particular failing of the model, and helps to keep the model bathymetry on track. It also improves the ability of the model to predict future bathymetry. Although the benefits of data assimilation are demonstrated using waterline observations, any observations of morphology could potentially be used. These results suggest that data assimilation should be considered for use in future coastal area morphodynamic models.

Deforming glassy polystyrene: Influence of pressure, thermal history, and deformation mode on yielding and hardening

The toughness of a polymer glass is determined by the interplay of yielding, strain softening, and strain hardening. Molecular-dynamics simulations of a typical polymer glass, atactic polystyrene, under the influence of active deformation have been carried out to enlighten these processes. It is observed that the dominant interaction for the yield peak is of interchain nature and for the strain hardening of intrachain nature. A connection is made with the microscopic cage-to-cage motion. It is found that the deformation does not lead to complete erasure of the thermal history but that differences persist at large length scales. Also we find that the strain-hardening modulus increases with increasing external pressure. This new observation cannot be explained by current theories such as the one based on the entanglement picture and the inclusion of this effect will lead to an improvement in constitutive modeling.

How many facets are needed to represent the surface energy balance of an urban area?

We investigate the question of how many facets are needed to represent the energy balance of an urban area by developing simplified 3-, 2- and 1-facet versions of a 4-facet energy balance model of two-dimensional streets and buildings. The 3-facet model simplifies the 4-facet model by averaging over the canyon orientation, which results in similar net shortwave and longwave balances for both wall facets, but maintains the asymmetry in the heat fluxes within the street canyon. For the 2-facet model, on the assumption that the wall and road temperatures are equal, the road and wall facets can be combined mathematically into a single street-canyon facet with effective values of the heat transfer coefficient, albedo, emissivity and thermodynamic properties, without further approximation. The 1-facet model requires the additional assumption that the roof temperature is also equal to the road and wall temperatures. Idealised simulations show that the geometry and material properties of the walls and road lead to a large heat capacity of the combined street canyon, whereas the roof behaves like a flat surface with low heat capacity. This means that the magnitude of the diurnal temperature variation of the street-canyon facets are broadly similar and much smaller than the diurnal temperature variation of the roof facets. Consequently, the approximation that the street-canyon facets have similar temperatures is sound, and the road and walls can be combined into a single facet. The roof behaves very differently and a separate roof facet is required. Consequently, the 2-facet model performs similarly to the 4-facet model, while the 1-facet model does not. The models are compared with previously published observations collected in Mexico City. Although the 3- and 2-facet models perform better than the 1-facet model, the present models are unable to represent the phase of the sensible heat flux. This result is consistent with previous model comparisons, and we argue that this feature of the data cannot be produced by a single column model. We conclude that a 2-facet model is necessary, and for numerical weather prediction sufficient, to model an urban surface, and that this conclusion is robust and therefore applicable to more general geometries.

North Atlantic subtropical mode waters and ocean memory in HadCM3

A study of the formation and propagation of volume anomalies in North Atlantic Mode Waters is presented, based on 100 yr of monthly mean fields taken from the control run of the Third Hadley Centre Coupled Ocean-Atmosphere GCM (HadCM3). Analysis of the temporal and. spatial variability in the thickness between pairs of isothermal surfaces bounding the central temperature of the three main North Atlantic subtropical mode waters shows that large-scale variability in formation occurs over time scales ranging from 5 to 20 yr. The largest formation anomalies are associated with a southward shift in the mixed layer isothermal distribution, possibly due to changes in the gyre dynamics and/or changes in the overlying wind field and air-sea heat fluxes. The persistence of these anomalies is shown to result from their subduction beneath the winter mixed layer base where they recirculate around the subtropical gyre in the background geostrophic flow. Anomalies in the warmest mode (18 degrees C) formed on the western side of the basin persist for up to 5 yr. They are removed by mixing transformation to warmer classes and are returned to the seasonal mixed layer near the Gulf Stream where the stored heat may be released to the atmosphere. Anomalies in the cooler modes (16 degrees and 14 degrees C) formed on the eastern side of the basin persist for up to 10 yr. There is no clear evidence of significant transformation of these cooler mode anomalies to adjacent classes. It has been proposed that the eastern anomalies are removed through a tropical-subtropical water mass exchange mechanism beneath the trade wind belt (south of 20 degrees N). The analysis shows that anomalous mode water formation plays a key role in the long-term storage of heat in the model, and that the release of heat associated with these anomalies suggests a predictable climate feedback mechanism.

The effect of a large freshwater perturbation on the glacial north Atlantic Ocean using a coupled general circulation model

The commonly held view of the conditions in the North Atlantic at the last glacial maximum, based on the interpretation of proxy records, is of large-scale cooling compared to today, limited deep convection, and extensive sea ice, all associated with a southward displaced and weakened overturning thermohaline circulation (THC) in the North Atlantic. Not all studies support that view; in particular, the "strength of the overturning circulation" is contentious and is a quantity that is difficult to determine even for the present day. Quasi-equilibrium simulations with coupled climate models forced by glacial boundary conditions have produced differing results, as have inferences made from proxy records. Most studies suggest the weaker circulation, some suggest little or no change, and a few suggest a stronger circulation. Here results are presented from a three-dimensional climate model, the Hadley Centre Coupled Model version 3 (HadCM3), of the coupled atmosphere - ocean - sea ice system suggesting, in a qualitative sense, that these diverging views could all have occurred at different times during the last glacial period, with different modes existing at different times. One mode might have been characterized by an active THC associated with moderate temperatures in the North Atlantic and a modest expanse of sea ice. The other mode, perhaps forced by large inputs of meltwater from the continental ice sheets into the northern North Atlantic, might have been characterized by a sluggish THC associated with very cold conditions around the North Atlantic and a large areal cover of sea ice. The authors' model simulation of such a mode, forced by a large input of freshwater, bears several of the characteristics of the Climate: Long-range Investigation, Mapping, and Prediction (CLIMAP) Project's reconstruction of glacial sea surface temperature and sea ice extent.

The effects of triazole and strobilurin fungicide programmes on nitrogen uptake, partitioning, remobilization and grain N accumulation in winter wheat cultivars

Field experiments were conducted over 3 years to assess the effect of a triazole fungicide programme, and additions of strobilurin fungicides to it, on nitrogen uptake, accumulation and partitioning in a range of winter wheat cultivars. Commensurate with delayed senescence, fungicide programmes, particularly when including strobilurins, improved grain yield through improvements in both crop biomass and harvest index, although the relationship with green area duration of the flag leaf (GFLAD) depended on year and in some cases, cultivar. In all years fungicide treatments significantly increased the amount of nitrogen in the above-ground biomass, the amount of nitrogen in the grain and the nitrogen harvest index. All these effects could be linearly related to the fungicide effect on GFLAD. These relationships occasionally interacted with cultivar but there was no evidence that fungicide mode of action affected the relationship between GFLAD and yield of nitrogen in the grain. Fungicide treatments significantly reduced the amount of soil mineral N at harvest and when severe disease had been controlled, the net remobilization of N from the vegetation to the grain after anthesis. Fungicide maintained the filling of grain with both dry matter and nitrogen. The proportionate accumulation of nitrogen in the grain was later than that of dry matter and this difference was greater when fungicide had been applied. Effects of fungicide on grain protein concentration and its relationship with GFLAD were inconsistent over year and cultivar. There were several instances where grain protein concentration was unaffected despite large (1(.)5 t/ha) increases in grain yield following fungicide use. Dilution of grain protein concentration following fungicide use, when it did occur, was small compared with what would be predicted by adoption of other yield increasing techniques such as the selection of high yielding cultivars (based on currently available cultivars) or by growing wheat in favourable climates.