Evaluation of biospheric components in Earth system models using modern and palaeo-observations: the state-of-the-art

Earth system models (ESMs) are increasing in complexity by incorporating more processes than their predecessors, making them potentially important tools for studying the evolution of climate and associated biogeochemical cycles. However, their coupled behaviour has only recently been examined in any detail, and has yielded a very wide range of outcomes. For example, coupled climate–carbon cycle models that represent land-use change simulate total land carbon stores at 2100 that vary by as much as 600 Pg C, given the same emissions scenario. This large uncertainty is associated with differences in how key processes are simulated in different models, and illustrates the necessity of determining which models are most realistic using rigorous methods of model evaluation. Here we assess the state-of-the-art in evaluation of ESMs, with a particular emphasis on the simulation of the carbon cycle and associated biospheric processes. We examine some of the new advances and remaining uncertainties relating to (i) modern and palaeodata and (ii) metrics for evaluation. We note that the practice of averaging results from many models is unreliable and no substitute for proper evaluation of individual models. We discuss a range of strategies, such as the inclusion of pre-calibration, combined process- and system-level evaluation, and the use of emergent constraints, that can contribute to the development of more robust evaluation schemes. An increasingly data-rich environment offers more opportunities for model evaluation, but also presents a challenge. Improved knowledge of data uncertainties is still necessary to move the field of ESM evaluation away from a "beauty contest" towards the development of useful constraints on model outcomes.

The trading profitability of forecasts of the gilt–equity yield ratio

Research has highlighted the usefulness of the Gilt–Equity Yield Ratio (GEYR) as a predictor of UK stock returns. This paper extends recent studies by endogenising the threshold at which the GEYR switches from being low to being high or vice versa, thus improving the arbitrary nature of the determination of the threshold employed in the extant literature. It is observed that a decision rule for investing in equities or bonds, based on the forecasts from a regime switching model, yields higher average returns with lower variability than a static portfolio containing any combinations of equities and bonds. A closer inspection of the results reveals that the model has power to forecast when investors should steer clear of equities, although the trading profits generated are insufficient to outweigh the associated transaction costs.

Solvent-Dependent Formation of Os(0) Complexes by Electrochemical Reduction of [Os(CO)(2,2′-bipyridine)(L)Cl2]; L = Cl−,PrCN

Cyclic voltammetry and ultraviolet−visible/infrared (UV−vis/IR) spectroelectrochemistry were used to study the cathodic electrochemical behavior of the osmium complexes mer-[OsIII(CO) (bpy)Cl3] (bpy = 2,2′-bipyridine) and trans(Cl)-[OsII(CO) (PrCN)(bpy)Cl2] at variable temperature in different solvents (tetrahydrofuran (THF), butyronitrile (PrCN), acetonitrile (MeCN)) and electrolytes (Bu4NPF6, Bu4NCl). The precursors can be reduced to mer-[OsII(CO) (bpy•−)Cl3]2− and trans(Cl)-[OsII(CO)(PrCN) (bpy•−)Cl2]−, respectively, which react rapidly at room temperature, losing the chloride ligands and forming Os(0) species. mer-[OsIII(CO) (bpy)Cl3] is reduced in THF to give ultimately an Os−Os-bonded polymer, probably [Os0(CO) (THF)-(bpy)]n, whereas in PrCN the well-soluble, probably mononuclear [Os0(CO) (PrCN)(bpy)], species is formed. The same products were observed for the 2 electron reduction of trans(Cl)-[OsII(CO)(PrCN) (bpy)Cl2] in both solvents. In MeCN, similar to THF, the[Os0(CO) (MeCN)(bpy)]n polymer is produced. It is noteworthy that the bpy ligand in mononuclear [Os0(CO) (PrCN)(bpy)] is reduced to the corresponding radical anion at a significantly less negative potential than it is in polymeric [Os0(CO) (THF)(bpy)]n: ΔE1/2 = 0.67 V. Major differences also exist in the IR spectra of the Os(0) species: the polymer shows a broad ν(CO) band at much smaller wavenumbers compared to the soluble Os(0) monomer that exhibits a characteristic ν(Pr-CN) band below 2200 cm−1 in addition to the intense and narrow ν(CO) absorption band. For the first time, in this work the M0-bpy(M = Ru, Os) mono- and dicarbonyl species soluble in PrCN have been formulated as a mononuclear complex. Density functional theory (DFT) and time-dependent-DFT calculations confirm the Os(0) oxidation state and suggest that [Os0(CO)(PrCN)(bpy)] is a square planar moiety. The reversible bpy-based reduction of [Os0(CO) (PrCN)(bpy)] triggers catalytic reduction of CO2 to CO and HCOO−.

Ring-opening polymerization in molten PEEK: transient reduction of melt-viscosity by macrocyclic aromatic thioetherketones

Blends of PEEK with macrocyclic thioether-ketones show initial melt-viscosities reduced by more than an order of magnitude relative to the polymer itself, enabling more facile processing and fabrication. On raising the temperature of the melt, however, the macrocycle undergoes spontaneous, entropically-driven ring-opening polymerization (ED-ROP), so that the properties of the final polymer should not, in principle, be compromised by the presence of low-MW macrocyclic material.

Electrocatalytic reduction of carbon dioxide with a manganese(I)tricarbonyl complex containing a nonaromatic α‑diimine ligand

The 2e reduced anion [Mn(CO)3(iPr-DAB)]− (DAB = 1,4- diazabuta-1,3-diene, iPr = isopropyl) was shown to convert in the presence of CO2 and a small amount of water to the unstable complex [Mn(CO)3(iPr-DAB)(η1-OCO2H)] (OCO2H− = unidentate bicarbonate) that was further reductively transformed to give a stable catalytic intermediate denoted as X2, showing νs(OCO) 1672 and 1646 (sh) cm−1. The subsequent cathodic shift by ca. 650 mV in comparison to the single 2e cathodic wave of the parent [Mn(CO)3(iPr-DAB)Br] triggers the reduction of intermediate X2 and catalytic activity converting CO2 to CO. Infrared spectroelectrochemistry has revealed that the high excess of CO generated at the cathode leads to the conversion of [Mn(CO)3(iPr-DAB)]− to inactive [Mn(CO)5]−. In contrast, the five-coordinate anion [Mn(CO)3(pTol-DAB)]−(pTol = 4-tolyl) is completely inert toward both CO2 and H2O (solvolysis). This detailed spectroelectrochemical study is a further contribution to the development of sustainable electro- and photoelectrocatalysts of CO2 reduction based on abundant first-row transition metals, in particular manganese.

Aerosol direct radiative effect of smoke over clouds over the southeast Atlantic Ocean from 2006 to 2009

The aerosol direct radiative effect (DRE) of African smoke was analyzed in cloud scenes over the southeast Atlantic Ocean, using Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) satellite observations and Hadley Centre Global Environmental Model version 2 (HadGEM2) climate model simulations. The observed mean DRE was about 30–35 W m−2 in August and September 2006–2009. In some years, short episodes of high-aerosol DRE can be observed, due to high-aerosol loadings, while in other years the loadings are lower but more prolonged. Climate models that use evenly distributed monthly averaged emission fields will not reproduce these high-aerosol loadings. Furthermore, the simulated monthly mean aerosol DRE in HadGEM2 is only about 6 W m−2 in August. The difference with SCIAMACHY mean observations can be partly explained by an underestimation of the aerosol absorption Ångström exponent in the ultraviolet. However, the subsequent increase of aerosol DRE simulation by about 20% is not enough to explain the observed discrepancy between simulations and observations.

[M(CO)4(2,2′-bipyridine)] (M = Cr, Mo, W) as efficient catalysts for electrochemical reduction of CO2 to CO at a gold electrode

Group 6 complexes of the type [M(CO)4(bpy)] (M=Cr, Mo, W) are capable of behaving as electrochemical catalysts for the reduction of CO2 at potentials less negative than those for the reduction of the radical anions [M(CO)4(bpy)].−. Cyclic voltammetric, chronoamperometric and UV/Vis/IR spectro-electrochemical data reveal that five-coordinate [M(CO)3(bpy)]2− are the active catalysts. The catalytic conversion is significantly more efficient in N-methyl-2-pyrrolidone (NMP) compared to tetrahydrofuran, which may reflect easier CO dissociation from 1e−-reduced [M(CO)4(bpy)].− in the former solvent, followed by second electron transfer. The catalytic cycle may also involve [M(CO)4(H-bpy)]− formed by protonation of [M(CO)3(bpy)]2−, especially in NMP. The strongly enhanced catalysis using an Au working electrode is remarkable, suggesting that surface interactions may play an important role, too.

Separating heart and brain: on the reduction of physiological noise from multichannel functional near-infrared spectroscopy (fNIRS) signals

Objective. Functional near-infrared spectroscopy (fNIRS) is an emerging technique for the in vivo assessment of functional activity of the cerebral cortex as well as in the field of brain–computer interface (BCI) research. A common challenge for the utilization of fNIRS in these areas is a stable and reliable investigation of the spatio-temporal hemodynamic patterns. However, the recorded patterns may be influenced and superimposed by signals generated from physiological processes, resulting in an inaccurate estimation of the cortical activity. Up to now only a few studies have investigated these influences, and still less has been attempted to remove/reduce these influences. The present study aims to gain insights into the reduction of physiological rhythms in hemodynamic signals (oxygenated hemoglobin (oxy-Hb), deoxygenated hemoglobin (deoxy-Hb)). Approach. We introduce the use of three different signal processing approaches (spatial filtering, a common average reference (CAR) method; independent component analysis (ICA); and transfer function (TF) models) to reduce the influence of respiratory and blood pressure (BP) rhythms on the hemodynamic responses. Main results. All approaches produce large reductions in BP and respiration influences on the oxy-Hb signals and, therefore, improve the contrast-to-noise ratio (CNR). In contrast, for deoxy-Hb signals CAR and ICA did not improve the CNR. However, for the TF approach, a CNR-improvement in deoxy-Hb can also be found. Significance. The present study investigates the application of different signal processing approaches to reduce the influences of physiological rhythms on the hemodynamic responses. In addition to the identification of the best signal processing method, we also show the importance of noise reduction in fNIRS data.

Protocol for a feasibility study of a self help cognitive behavioural therapy resource for the reduction of dental anxiety in young people

Background Childhood dental anxiety is very common, with 10–20 % of children and young people reporting high levels of dental anxiety. It is distressing and has a negative impact on the quality of life of young people and their parents as well as being associated with poor oral health. Affected individuals may develop a lifelong reliance on general anaesthetic or sedation for necessary dental treatment thus requiring the support of specialist dental services. Children and young people with dental anxiety therefore require additional clinical time and can be costly to treat in the long term. The reduction of dental anxiety through the use of effective psychological techniques is, therefore, of high importance. However, there is a lack of high-quality research investigating the impact of cognitive behavioural therapy (CBT) approaches when applied to young people’s dental anxiety. Methods/design The first part of the study will develop a profile of dentally anxious young people using a prospective questionnaire sent to a consecutive sample of 100 young people referred to the Paediatric Dentistry Department, Charles Clifford Dental Hospital, in Sheffield. The second part will involve interviewing a purposive sample of 15–20 dental team members on their perceptions of a CBT self-help resource for dental anxiety, their opinions on whether they might use such a resource with patients, and their willingness to recruit participants to a future randomised controlled trial (RCT) to evaluate the resource. The third part of the study will investigate the most appropriate outcome measures to include in a trial, the acceptability of the resource, and retention and completion rates of treatment with a sample of 60 dentally anxious young people using the CBT resource. Discussion This study will provide information on the profile of dentally anxious young people who could potentially be helped by a guided self-help CBT resource. It will gain the perceptions of dental care team members of guided self-help CBT for dental anxiety in young people and their willingness to recruit participants to a trial. Acceptability of the resource to participants and retention and completion rates will also be investigated to inform a future RCT.

Secoiridoids delivered as olive leaf extract induce acute improvements in human vascular function and reduction of an inflammatory cytokine: a randomised, double-blind, placebo-controlled, cross-over trial

The leaves of the olive plant (Olea europaea) are rich in polyphenols, of which oleuropein and hydroxytyrosol (HT) are most characteristic. Such polyphenols have been demonstrated to favourably modify a variety of cardiovascular risk factors. The aim of the present intervention was to investigate the influence of olive leaf extract (OLE) on vascular function and inflammation in a postprandial setting and to link physiological outcomes with absorbed phenolics. A randomised, double-blind, placebo-controlled, cross-over, acute intervention trial was conducted with eighteen healthy volunteers (nine male, nine female), who consumed either OLE (51 mg oleuropein; 10mg HT), or a matched control (separated by a 4-week wash out) on a single occasion. Vascular function was measured by digital volume pulse (DVP), while blood collected at baseline, 1, 3 and 6 h was cultured for 24 h in the presence of lipopolysaccharide in order to investigate effects on cytokine production. Urine was analysed for phenolic metabolites by HPLC. DVP-stiffness index and ex vivo IL-8 production were significantly reduced (P < 0.05) after consumption of OLE compared to the control. These effects were accompanied by the excretion of several phenolic metabolites, namely HT and oleuropein derivatives, which peaked in urine after 8-24 h. The present study provides the first evidence that OLE positively modulates vascular function and IL-8 production in vivo, adding to growing evidence that olive phenolics could be beneficial for health.

Simulation of crop yields using ERA-40: Limits to skill and nonstationarity in weather-yield relationships

Reanalysis data provide an excellent test bed for impacts prediction systems. because they represent an upper limit on the skill of climate models. Indian groundnut (Arachis hypogaea L.) yields have been simulated using the General Large-Area Model (GLAM) for annual crops and the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-yr reanalysis (ERA-40). The ability of ERA-40 to represent the Indian summer monsoon has been examined. The ability of GLAM. when driven with daily ERA-40 data, to model both observed yields and observed relationships between subseasonal weather and yield has been assessed. Mean yields "were simulated well across much of India. Correlations between observed and modeled yields, where these are significant. are comparable to correlations between observed yields and ERA-40 rainfall. Uncertainties due to the input planting window, crop duration, and weather data have been examined. A reduction in the root-mean-square error of simulated yields was achieved by applying bias correction techniques to the precipitation. The stability of the relationship between weather and yield over time has been examined. Weather-yield correlations vary on decadal time scales. and this has direct implications for the accuracy of yield simulations. Analysis of the skewness of both detrended yields and precipitation suggest that nonclimatic factors are partly responsible for this nonstationarity. Evidence from other studies, including data on cereal and pulse yields, indicates that this result is not particular to groundnut yield. The detection and modeling of nonstationary weather-yield relationships emerges from this study as an important part of the process of understanding and predicting the impacts of climate variability and change on crop yields.

Use of mutants to dissect the role of ethylene signalling in organ senescence and the regulation of yield in Arabidopsis thaliana

The role of ethylene in regulating organ senescence in Arabidopsis has been investigated by studying the development of mutants that have an attenu- ated capacity to perceive the gas. The onset of leaf senescence and floral organ abscission was delayed in the ethylene-insensitive mutant etr1. The photosynthetic life span of rosette leaves was similarly extended in the gain- of-function mutant ers2, and this mutant also exhibited a delay in the timing of pod dehiscence primarily as a con- sequence of an extension in the final stages of senescence. A detailed analysis of yield revealed that whilst thousand grain weight was increased, by as much as 20 %, in etr1, ein4, and the loss-of-function mutant etr2, only the latter showed a significant increase in total weight of seeds produced per plant. The other studied mutants exhibited a reduction in total seed yield of almost 40 %. These observations are discussed in the context of the possible role of ethylene in regulating organ senescence and their significance in the breeding of crop plants with enhanced phenotypic characteristics.

Flavour characterization of fresh and processed pennywort (Centella asiatica L.) juices

The flavour characteristics of fresh and processed pennywort juices treated by pasteurization, sterilization and high pressure processing (HPP) were investigated by using solid-phase micro-extraction combined with gas chromatography-mass spectrometry. Sesquiterpene hydrocarbons comprised the major class of volatile components present and the juices had a characteristic smell due to the presence of volatile compounds including β-caryophyllene, humulene, E-β-farnesene, α-copaene, alloaromadendrene and β-elemene. All processing operations caused a reduction in the total volatile concentration, but HPP caused more volatile acyclic alcohols, aldehydes and oxygenated monoterpenoids to be retained than pasteurization and sterilization. Ketones were not present in fresh pennywort juice, but 2-butanone and 3-nonen-2-one were generated in all processed juices, and 2-nonanone and 2-hexanone were present in pasteurized and sterilized juices. Other chemical changes including isomerization were also reduced by HPP compared to pasteurization, and sterilization.

Probabilistic simulations of crop yield over western India using the DEMETER seasonal hindcast ensembles

Process-based integrated modelling of weather and crop yield over large areas is becoming an important research topic. The production of the DEMETER ensemble hindcasts of weather allows this work to be carried out in a probabilistic framework. In this study, ensembles of crop yield (groundnut, Arachis hypogaea L.) were produced for 10 2.5 degrees x 2.5 degrees grid cells in western India using the DEMETER ensembles and the general large-area model (GLAM) for annual crops. Four key issues are addressed by this study. First, crop model calibration methods for use with weather ensemble data are assessed. Calibration using yield ensembles was more successful than calibration using reanalysis data (the European Centre for Medium-Range Weather Forecasts 40-yr reanalysis, ERA40). Secondly, the potential for probabilistic forecasting of crop failure is examined. The hindcasts show skill in the prediction of crop failure, with more severe failures being more predictable. Thirdly, the use of yield ensemble means to predict interannual variability in crop yield is examined and their skill assessed relative to baseline simulations using ERA40. The accuracy of multi-model yield ensemble means is equal to or greater than the accuracy using ERA40. Fourthly, the impact of two key uncertainties, sowing window and spatial scale, is briefly examined. The impact of uncertainty in the sowing window is greater with ERA40 than with the multi-model yield ensemble mean. Subgrid heterogeneity affects model accuracy: where correlations are low on the grid scale, they may be significantly positive on the subgrid scale. The implications of the results of this study for yield forecasting on seasonal time-scales are as follows. (i) There is the potential for probabilistic forecasting of crop failure (defined by a threshold yield value); forecasting of yield terciles shows less potential. (ii) Any improvement in the skill of climate models has the potential to translate into improved deterministic yield prediction. (iii) Whilst model input uncertainties are important, uncertainty in the sowing window may not require specific modelling. The implications of the results of this study for yield forecasting on multidecadal (climate change) time-scales are as follows. (i) The skill in the ensemble mean suggests that the perturbation, within uncertainty bounds, of crop and climate parameters, could potentially average out some of the errors associated with mean yield prediction. (ii) For a given technology trend, decadal fluctuations in the yield-gap parameter used by GLAM may be relatively small, implying some predictability on those time-scales.

Effect of replacing calcium salts of palm oil distillate with extruded linseeds on milk fatty acid composition in Jersey and Holstein cows

Clinical and biomedical studies have provided evidence for the critical role of n-3 fatty acids on the reduction of chronic disease risk in humans, including cardiovascular disease. In the current experiment, the potential to enhance milk n-3 content in two breeds with inherent genetic differences in mammary lipogenesis and de novo fatty acid synthesis was examined using extruded linseeds. Six lactating cows (three Holstein and three Jersey) were used in a two-treatment switchback design with 3 × 21-day experimental periods to evaluate the effect of iso-energetic replacement of calcium salts of palm oil distillate (CPO) in the diet (34 g/kg dry matter (DM)) with 100 g/kg DM extruded linseeds (LIN). For both breeds, replacing CPO with LIN had no effect (P > 0.05) on DM intake or milk yield, but reduced (P < 0.05) milk fat and protein yield (on average, from 760 to 706 and 573 to 552 g/day, respectively). Relative to CPO, the LIN treatment reduced (P < 0.01) total saturated fatty acid content and enhanced (P < 0.001) 18:3n-3 in milk, whereas breed by diet interactions were significant for milk fat 16:0, total trans fatty acid and conjugated linoleic acid concentrations. Increases in 18:3n-3 intake derived from LIN in the diet were transferred into milk with a mean marginal transfer efficiency of 1.8%. Proportionate changes in milk fatty acid composition were greater in the Jersey, highlighting the importance of diet–genotype interactions on mammary lipogenesis. More extensive studies are required to determine the role of genotype on milk fat composition responses to oilseeds in the diet.