New results on the thermodynamical properties of the climate system

In this paper the authors exploit two equivalent formulations of the average rate of material entropy production in the climate system to propose an approximate splitting between contributions due to vertical and eminently horizontal processes. This approach is based only on 2D radiative fields at the surface and at the top of atmosphere. Using 2D fields at the top of atmosphere alone, lower bounds to the rate of material entropy production and to the intensity of the Lorenz energy cycle are derived. By introducing a measure of the efficiency of the planetary system with respect to horizontal thermodynamic processes, it is possible to gain insight into a previous intuition on the possibility of defining a baroclinic heat engine extracting work from the meridional heat flux. The approximate formula of the material entropy production is verified and used for studying the global thermodynamic properties of climate models (CMs) included in the Program for Climate Model Diagnosis and Intercomparison (PCMDI)/phase 3 of the Coupled Model Intercomparison Project (CMIP3) dataset in preindustrial climate conditions. It is found that about 90% of the material entropy production is due to vertical processes such as convection, whereas the large-scale meridional heat transport contributes to only about 10% of the total. This suggests that the traditional two-box models used for providing a minimal representation of entropy production in planetary systems are not appropriate, whereas a basic—but conceptually correct—description can be framed in terms of a four-box model. The total material entropy production is typically 55 mW m−2 K−1, with discrepancies on the order of 5%, and CMs’ baroclinic efficiencies are clustered around 0.055. The lower bounds on the intensity of the Lorenz energy cycle featured by CMs are found to be around 1.0–1.5 W m−2, which implies that the derived inequality is rather stringent. When looking at the variability and covariability of the considered thermodynamic quantities, the agreement among CMs is worse, suggesting that the description of feedbacks is more uncertain. The contributions to material entropy production from vertical and horizontal processes are positively correlated, so that no compensation mechanism seems in place. Quite consistently among CMs, the variability of the efficiency of the system is a better proxy for variability of the entropy production due to horizontal processes than that of the large-scale heat flux. The possibility of providing constraints on the 3D dynamics of the fluid envelope based only on 2D observations of radiative fluxes seems promising for the observational study of planets and for testing numerical models.

A flow system for the on-line quantitative measurement of the retention of dosage forms on biological surfaces using spectroscopy and image analysis

Measuring the retention, or residence time, of dosage forms to biological tissue is commonly a qualitative measurement, where no real values to describe the retention can be recorded. The result of this is an assessment that is dependent upon a user's interpretation of visual observation. This research paper outlines the development of a methodology to quantitatively measure, both by image analysis and by spectrophotometric techniques, the retention of material to biological tissues, using the retention of polymer solutions to ocular tissue as an example. Both methods have been shown to be repeatable, with the spectrophotometric measurement generating data reliably and quickly for further analysis.

Pedosedimentary, cultural and environmental significance of palaeosols within Pre-Hispanic agricultural terraces in the southern Peruvian Andes

Paleosols were exposed in sections through four abandoned pre-Hispanic agricultural terraces surrounding an infilled mire basin in the southern Peruvian Andes. The two paleosols beneath the Tocotoccasa terrace represent the original ‘natural’ solum and a later soil formed after construction of the agricultural terrace, probably during the early Middle Horizon cultural period (615–695 AD). The soil at the current surface developed subsequent to the building up and reconstruction of the terrace, possibly during the late Late Intermediate period (1200–1400 AD). Micromorphology revealed an unexpected abundance of clay coatings within the upper terrace paleosol and surface terrace soil, a phenonemon attributed to the migration and/or accumulation of neoformed clay produced from the weathering of very unstable volcanic clasts, perhaps fuelled by arid/humid climatic oscillations and/or seasonal input of irrigation waters. The paleosols at Tocotoccasa could not be correlated with any degree of confidence with those beneath the other three terraces due to differences in pedosedimentary properties and uncertainties over chronological controls. Thus, it seems likely that either the terraces were (re)constructed and utilised over different cultural periods or that there is significant variation in the extent of weathering of material used for reconstruction of the terraces. Unfortunately, it cannot be ascertained from the data available whether the terraces were abandoned for any significant period of time prior to reconstruction and, if so, whether this was a regional phenomenon related to climate, social, or economic changes.

Characterization of safe nanostructured polymeric materials

The addition of small quantities of nanoparticles to conventional and sustainable thermoplastics leads to property enhancements with considerable potential in many areas of applications including food packaging 1, lightweight composites and high performance materials 2. In the case of sustainable polymers 3, the addition of nanoparticles may well sufficiently enhance properties such that the portfolio of possible applications is greatly increased. Most engineered nanoparticles are highly stable and these exist as nanoparticles prior to compounding with the polymer resin. They remain as nanoparticles during the active use of the packaging material as well as in the subsequent waste and recycling streams. It is also possible to construct the nanoparticles within the polymer films during processing from organic compounds selected to present minimal or no potential health hazards 4. In both cases the characterisation of the resultant nanostructured polymers presents a number of challenges. Foremost amongst these are the coupled challenges of the nanoscale of the particles and the low fraction present in the polymer matrix. Very low fractions of nanoparticles are only effective if the dispersion of the particles is good. This continues to be an issue in the process engineering but of course bad dispersion is much easier to see than good dispersion. In this presentation we show the merits of a combined scattering (neutron and x-ray) and microscopy (SEM, TEM, AFM) approach. We explore this methodology using rod like, plate like and spheroidal particles including metallic particles, plate-like and rod-like clay dispersions and nanoscale particles based on carbon such as nanotubes and graphene flakes. We will draw on a range of material systems, many explored in partnership with other members of Napolynet. The value of adding nanoscale particles is that the scale matches the scale of the structure in the polymer matrix. Although this can lead to difficulties in separating the effects in scattering experiments, the result in morphological studies means that both the nanoparticles and the polymer morphology are revealed.

Elevated levels of corticotrophin-releasing factor binding protein in the blood of patients suffering from arthritis and septicaemia and the presence of novel ligands in synovial fluid.

In view of the reported inflammatory effects of corticotrophin-releasing factor (CRF) and the associated regulatory elements in the gene of its binding protein (BP), we postulate that both BP as well as novel BP-ligands other than CRF may be involved in inflammatory disease. We have investigated BP in the blood of patients with arthritis and septicaemia and have attempted to identify CRF and other BP-ligands in synovial fluid. The BP was found to be significantly elevated in the blood of patients with rheumatoid arthritis and septicaemia. There was less BP-ligand and CRF in synovial fluid from patients with rheumatoid arthritis that from those with osteo- or psoriatic arthritis. There was at least 10-fold more BP-ligand than CRF in the fluid of all three groups of patients. A small amount of immunoreactive human (h)CRF, eluting in the expected position of CRF-41, was detected after high-pressure liquid chromatography of arthritic synovial fluid; however, the bulk of material with BP-ligand binding activity eluted earlier, suggesting that synovial fluid contained novel peptides that interacted with the BP. These results would suggest that the BP and its ligands could play an endocrine immunomodulatory role in inflammatory disease.

Preparation of films of a highly aligned lipid cubic phase

We demonstrate a method by which we can produce an oriented film of an inverse bicontinuous cubic phase (QII D) formed by the lipid monoolein (MO). By starting with the lipid as a disordered precursor (the L3 phase) in the presence of butanediol, we can obtain a film of the QII D phase showing a high degree of in-plane orientation by controlled dilution of the sample under shear within a linear flow cell. We demonstrate that the direction of orientation of the film is different from that found in the oriented bulk material that we have reported previously; therefore, we can now reproducibly form QII D samples oriented with either the [110] or the [100] axis aligned in the flow direction depending on the method of preparation. The deposition of MO as a film, via a moving fluid− air interface that leaves a coating of MO in the L3 phase on the capillary wall, leads to a sample in the [110] orientation. This contrasts with the bulk material that we have previously demonstrated to be oriented in the [100] direction, arising from flow producing an oriented bulk slug of material within the capillary tube. The bulk sample contains significant amounts of residual butanediol, which can be estimated from the lattice parameter of the QII D phase obtained. The sample orientation and lattice parameters are determined from synchrotron small-angle X-ray scattering patterns and confirmed by simulations. This has potential applications in the production of template materials and the growth of protein crystals for crystallography as well as deepening our understanding of the mechanisms underlying the behavior of lyotropic liquid-crystal phases.

Flow structure and near-field dispersion in arrays of building-like obstacles

Dispersion in the near-field region of localised releases in urban areas is difficult to predict because of the strong influence of individual buildings. Effects include upstream dispersion, trapping of material into building wakes and enhanced concentration fluctuations. As a result, concentration patterns are highly variable in time and mean profiles in the near field are strongly non-Gaussian. These aspects of near-field dispersion are documented by analysing data from direct numerical simulations in arrays of building-like obstacles and are related to the underlying flow structure. The mean flow structure around the buildings is found to exert a strong influence over the dispersion of material in the near field. Diverging streamlines around buildings enhance lateral dispersion. Entrainment of material into building wakes in the very near field gives rise to secondary sources, which then affect the subsequent dispersion pattern. High levels of concentration fluctuations are also found in this very near field; the fluctuation intensity is of order 2 to 5.

Ozonolysis of methyl oleate monolayers at the air–water interface: oxidation kinetics, reaction products and atmospheric implications

Ozonolysis of methyl oleate monolayers at the air–water interface results in surprisingly rapid loss of material through cleavage of the C[double bond, length as m-dash]C bond and evaporation/dissolution of reaction products. We determine using neutron reflectometry a rate coefficient of (5.7 ± 0.9) × 10−10 cm2 molecule−1 s−1 and an uptake coefficient of [similar]3 × 10−5 for the oxidation of a methyl ester monolayer: the atmospheric lifetime is [similar]10 min. We obtained direct experimental evidence that <2% of organic material remains at the surface on atmospheric timescales. Therefore known long atmospheric residence times of unsaturated fatty acids suggest that these molecules cannot be present at the interface throughout their ageing cycle, i.e. the reported atmospheric longevity is likely to be attributed to presence in the bulk and viscosity-limited reactive loss. Possible reaction products were characterized by ellipsometry and uncertainties in the atmospheric fate of organic surfactants such as oleic acid and its methyl ester are discussed. Our results suggest that a minor change to the structure of the molecule (fatty acid vs. its methyl ester) considerably impacts on reactivity and fate of the organic film.

Re-fitting Etton: space, time and material culture within a causewayed enclosure in Cambridgeshire

This paper considers the dynamics of deposition around and across the causewayed enclosure at Etton, Cambridgeshire. As a result of detailed re-analysis (particularly refitting) of the pottery and flint assemblages from the site, it proved possible to shed new light both on the temporality of occupation and the character of deposition there. Certain aspects of our work challenge previous interpretations of the site, and of causewayed enclosures in general; but, just as importantly, others confirm materially what has previously been suggested. The quantities of material deposited at Etton reveal that the enclosure was occupied only very intermittently and certainly less regularly than other contemporary sites in the region. The spatial distribution of material suggests that the enclosure ditch lay open for the entirety of the monument's life, but that acts of deposition generally focused on a specific part of the monument at any one time. As well as enhancing our knowledge of one particular causewayed enclosure, it is hoped that this paper – in combination with our earlier analysis of the pit site at Kilverstone – makes clear the potential that detailed material analysis has to offer in relation to our understanding of the temporality of occupation on prehistoric sites in general.

Rapid, automated detection of stem canker symptoms in woody perennials using artificial neural network analysis

Background Pseudomonas syringae can cause stem necrosis and canker in a wide range of woody species including cherry, plum, peach, horse chestnut and ash. The detection and quantification of lesion progression over time in woody tissues is a key trait for breeders to select upon for resistance. Results In this study a general, rapid and reliable approach to lesion quantification using image recognition and an artificial neural network model was developed. This was applied to screen both the virulence of a range of P. syringae pathovars and the resistance of a set of cherry and plum accessions to bacterial canker. The method developed was more objective than scoring by eye and allowed the detection of putatively resistant plant material for further study. Conclusions Automated image analysis will facilitate rapid screening of material for resistance to bacterial and other phytopathogens, allowing more efficient selection and quantification of resistance responses.

Up-scaled synthesis process of sulphur-based thermoelectric materials

The scale up of Spark Plasma Sintering (SPS) for the consolidation of large square monoliths (50 × 50 × 3 mm3) of thermoelectric material is demonstrated and the properties of the fabricated samples compared with those from laboratory scale SPS. The SPS processing of n-type TiS2 and p-type Cu10.4Ni1.6Sb4S13 produces highly dense compacts of phase pure material. Electrical and thermal transport property measurements reveal that the thermoelectric performance of the consolidated n- and p-type materials is comparable with that of material processed using laboratory scale SPS, with ZT values that approach 0.8 and 0.35 at 700 K for Cu10.4Ni1.6Sb4S13 and TiS2, respectively. Mechanical properties of the consolidated materials shows that large-scale SPS processing produces highly homogeneous materials with hardness and elastic moduli that deviate little from values obtained on materials processed on the laboratory scale.