On the difficulties of present theoretical models to predict the oxidation state of atomic Au adsorbed on regular sites of CeO2(111)

The electronic structure and oxidation state of atomic Au adsorbed on a perfect CeO2(111) surface have been investigated in detail by means of periodic density functional theory-based calculations, using the LDA+U and GGA+U potentials for a broad range of U values, complemented with calculations employing the HSE06 hybrid functional. In addition, the effects of the lattice parameter a0 and of the starting point for the geometry optimization have also been analyzed. From the present results we suggest that the oxidation state of single Au atoms on CeO2(111) predicted by LDA+U, GGA+U, and HSE06 density functional calculations is not conclusive and that the final picture strongly depends on the method chosen and on the construction of the surface model. In some cases we have been able to locate two well-defined states which are close in energy but with very different electronic structure and local geometries, one with Au fully oxidized and one with neutral Au. The energy difference between the two states is typically within the limits of the accuracy of the present exchange-correlation potentials, and therefore, a clear lowest-energy state cannot be identified. These results suggest the possibility of a dynamic distribution of Au0 and Au+ atomic species at the regular sites of the CeO2(111) surface.

Dopant-vacancy binding effects in Li-doped magnesium hydride

We use a combination of ab initio calculations and statistical mechanics to investigate the substitution of Li+ for Mg2+ in magnesium hydride (MgH2) accompanied by the formation of hydrogen vacancies with positive charge (with respect to the original ion at the site). We show that the binding energy between dopants and vacancy defects leads to a significant fraction of trapped vacancies and therefore a dramatic reduction in the number of free vacancies available for diffusion. The concentration of free vacancies initially increases with dopant concentration but reaches a maximum at around 1 mol % Li doping and slowly decreases with further doping. At the optimal level of doping, the corresponding concentration of free vacancies is much higher than the equilibrium concentrations of charged and neutral vacancies in pure MgH2 at typical hydrogen storage conditions. We also show that Li-doped MgH2 is thermodynamically metastable with respect to phase separation into pure magnesium and lithium hydrides at any significant Li concentration, even after considering the stabilization provided by dopant-vacancy interactions and configurational entropic effects. Our results suggest that lithium doping may enhance hydrogen diffusion hydride but only to a limited extent determined by an optimal dopant concentration and conditioned to the stability of the doped phase.

Building the niche through time: using 13,000 years of data to predict the effects of climate change on three tree species in Europe

Aim  Species distribution models (SDMs) based on current species ranges underestimate the potential distribution when projected in time and/or space. A multi-temporal model calibration approach has been suggested as an alternative, and we evaluate this using 13,000 years of data. Location  Europe. Methods  We used fossil-based records of presence for Picea abies, Abies alba and Fagus sylvatica and six climatic variables for the period 13,000 to 1000 yr bp. To measure the contribution of each 1000-year time step to the total niche of each species (the niche measured by pooling all the data), we employed a principal components analysis (PCA) calibrated with data over the entire range of possible climates. Then we projected both the total niche and the partial niches from single time frames into the PCA space, and tested if the partial niches were more similar to the total niche than random. Using an ensemble forecasting approach, we calibrated SDMs for each time frame and for the pooled database. We projected each model to current climate and evaluated the results against current pollen data. We also projected all models into the future. Results  Niche similarity between the partial and the total-SDMs was almost always statistically significant and increased through time. SDMs calibrated from single time frames gave different results when projected to current climate, providing evidence of a change in the species realized niches through time. Moreover, they predicted limited climate suitability when compared with the total-SDMs. The same results were obtained when projected to future climates. Main conclusions  The realized climatic niche of species differed for current and future climates when SDMs were calibrated considering different past climates. Building the niche as an ensemble through time represents a way forward to a better understanding of a species' range and its ecology in a changing climate.

Aerosol indirect effects – general circulation model intercomparison and evaluation with satellite data

Aerosol indirect effects continue to constitute one of the most important uncertainties for anthropogenic climate perturbations. Within the international AEROCOM initiative, the representation of aerosol-cloud-radiation interactions in ten different general circulation models (GCMs) is evaluated using three satellite datasets. The focus is on stratiform liquid water clouds since most GCMs do not include ice nucleation effects, and none of the model explicitly parameterises aerosol effects on convective clouds. We compute statistical relationships between aerosol optical depth (τa) and various cloud and radiation quantities in a manner that is consistent between the models and the satellite data. It is found that the model-simulated influence of aerosols on cloud droplet number concentration (Nd ) compares relatively well to the satellite data at least over the ocean. The relationship between �a and liquid water path is simulated much too strongly by the models. This suggests that the implementation of the second aerosol indirect effect mainly in terms of an autoconversion parameterisation has to be revisited in the GCMs. A positive relationship between total cloud fraction (fcld) and �a as found in the satellite data is simulated by the majority of the models, albeit less strongly than that in the satellite data in most of them. In a discussion of the hypotheses proposed in the literature to explain the satellite-derived strong fcld–�a relationship, our results indicate that none can be identified as a unique explanation. Relationships similar to the ones found in satellite data between �a and cloud top temperature or outgoing long-wave radiation (OLR) are simulated by only a few GCMs. The GCMs that simulate a negative OLR - �a relationship show a strong positive correlation between �a and fcld. The short-wave total aerosol radiative forcing as simulated by the GCMs is strongly influenced by the simulated anthropogenic fraction of �a, and parameterisation assumptions such as a lower bound on Nd . Nevertheless, the strengths of the statistical relationships are good predictors for the aerosol forcings in the models. An estimate of the total short-wave aerosol forcing inferred from the combination of these predictors for the modelled forcings with the satellite-derived statistical relationships yields a global annual mean value of −1.5±0.5Wm−2. In an alternative approach, the radiative flux perturbation due to anthropogenic aerosols can be broken down into a component over the cloud-free portion of the globe (approximately the aerosol direct effect) and a component over the cloudy portion of the globe (approximately the aerosol indirect effect). An estimate obtained by scaling these simulated clearand cloudy-sky forcings with estimates of anthropogenic �a and satellite-retrieved Nd–�a regression slopes, respectively, yields a global, annual-mean aerosol direct effect estimate of −0.4±0.2Wm−2 and a cloudy-sky (aerosol indirect effect) estimate of −0.7±0.5Wm−2, with a total estimate of −1.2±0.4Wm−2.

PPARGC1A sequence variation and cardiovascular risk-factor levels: a study of the main genetic effects and gene x environment interactions in children from the European Youth Heart Study.

AIMS/HYPOTHESIS: The PPARGC1A gene coactivates multiple nuclear transcription factors involved in cellular energy metabolism and vascular stasis. In the present study, we genotyped 35 tagging polymorphisms to capture all common PPARGC1A nucleotide sequence variations and tested for association with metabolic and cardiovascular traits in 2,101 Danish and Estonian boys and girls from the European Youth Heart Study, a multicentre school-based cross-sectional cohort study. METHODS: Fasting plasma glucose concentrations, anthropometric variables and blood pressure were measured. Habitual physical activity and aerobic fitness were objectively assessed using uniaxial accelerometry and a maximal aerobic exercise stress test on a bicycle ergometer, respectively. RESULTS: In adjusted models, nominally significant associations were observed for BMI (rs10018239, p = 0.039), waist circumference (rs7656250, p = 0.012; rs8192678 [Gly482Ser], p = 0.015; rs3755863, p = 0.02; rs10018239, beta = -0.01 cm per minor allele copy, p = 0.043), systolic blood pressure (rs2970869, p = 0.018) and fasting glucose concentrations (rs11724368, p = 0.045). Stronger associations were observed for aerobic fitness (rs7656250, p = 0.005; rs13117172, p = 0.008) and fasting glucose concentrations (rs7657071, p = 0.002). None remained significant after correcting for the number of statistical comparisons. We proceeded by testing for gene x physical activity interactions for the polymorphisms that showed nominal evidence of association in the main effect models. None of these tests was statistically significant. CONCLUSIONS/INTERPRETATION: Variants at PPARGC1A may influence several metabolic traits in this European paediatric cohort. However, variation at PPARGC1A is unlikely to have a major impact on cardiovascular or metabolic health in these children.

HDAC inhibitors attenuate the development of hypersensitivity in models of neuropathic pain

Histone deacetylase inhibitors (HDACIs) interfere with the epigenetic process of histone acetylation and are known to have analgesic properties in models of chronic inflammatory pain. The aim of this study was to determine whether these compounds could also affect neuropathic pain. Different class I HDACIs were delivered intrathecally into rat spinal cord in models of traumatic nerve injury and antiretroviral drug-induced peripheral neuropathy (stavudine, d4T). Mechanical and thermal hypersensitivity was attenuated by 40% to 50% as a result of HDACI treatment, but only if started before any insult. The drugs globally increased histone acetylation in the spinal cord, but appeared to have no measurable effects in relevant dorsal root ganglia in this treatment paradigm, suggesting that any potential mechanism should be sought in the central nervous system. Microarray analysis of dorsal cord RNA revealed the signature of the specific compound used (MS-275) and suggested that its main effect was mediated through HDAC1. Taken together, these data support a role for histone acetylation in the emergence of neuropathic pain.

Linking urban water balance and energy balance models to analyse urban design options

Using a water balance modelling framework, this paper analyses the effects of urban design on the water balance, with a focus on evapotranspiration and storm water. First, two quite different urban water balance models are compared: Aquacycle which has been calibrated for a suburban catchment in Canberra, Australia, and the single-source urban evapotranspiration-interception scheme (SUES), an energy-based approach with a biophysically advanced representation of interception and evapotranspiration. A fair agreement between the two modelled estimates of evapotranspiration was significantly improved by allowing the vegetation cover (leaf area index, LAI) to vary seasonally, demonstrating the potential of SUES to quantify the links between water sensitive urban design and microclimates and the advantage of comparing the two modelling approaches. The comparison also revealed where improvements to SUES are needed, chiefly through improved estimates of vegetation cover dynamics as input to SUES, and more rigorous parameterization of the surface resistance equations using local-scale suburban flux measurements. Second, Aquacycle is used to identify the impact of an array of water sensitive urban design features on the water balance terms. This analysis confirms the potential to passively control urban microclimate by suburban design features that maximize evapotranspiration, such as vegetated roofs. The subsequent effects on daily maximum air temperatures are estimated using an atmospheric boundary layer budget. Potential energy savings of about 2% in summer cooling are estimated from this analysis. This is a clear ‘return on investment’ of using water to maintain urban greenspace, whether as parks distributed throughout an urban area or individual gardens or vegetated roofs.

The effects of rotation and ice shelf topography on frazil-laden ice shelf water plumes

A model of the dynamics and thermodynamics of a plume of meltwater at the base of an ice shelf is presented. Such ice shelf water plumes may become supercooled and deposit marine ice if they rise (because of the pressure decrease in the in situ freezing temperature), so the model incorporates both melting and freezing at the ice shelf base and a multiple-size-class model of frazil ice dynamics and deposition. The plume is considered in two horizontal dimensions, so the influence of Coriolis forces is incorporated for the first time. It is found that rotation is extremely influential, with simulated plumes flowing in near-geostrophy because of the low friction at a smooth ice shelf base. As a result, an ice shelf water plume will only rise and become supercooled (and thus deposit marine ice) if it is constrained to flow upslope by topography. This result agrees with the observed distribution of marine ice under Filchner–Ronne Ice Shelf, Antarctica. In addition, it is found that the model only produces reasonable marine ice formation rates when an accurate ice shelf draft is used, implying that the characteristics of real ice shelf water plumes can only be captured using models with both rotation and a realistic topography.

Effects of temporal resolution of input precipitation on the performance of hydrological forecasting

Flood prediction systems rely on good quality precipitation input data and forecasts to drive hydrological models. Most precipitation data comes from daily stations with a good spatial coverage. However, some flood events occur on sub-daily time scales and flood prediction systems could benefit from using models calibrated on the same time scale. This study compares precipitation data aggregated from hourly stations (HP) and data disaggregated from daily stations (DP) with 6-hourly forecasts from ECMWF over the time period 1 October 2006–31 December 2009. The HP and DP data sets were then used to calibrate two hydrological models, LISFLOOD-RR and HBV, and the latter was used in a flood case study. The HP scored better than the DP when evaluated against the forecast for lead times up to 4 days. However, this was not translated in the same way to the hydrological modelling, where the models gave similar scores for simulated runoff with the two datasets. The flood forecasting study showed that both datasets gave similar hit rates whereas the HP data set gave much smaller false alarm rates (FAR). This indicates that using sub-daily precipitation in the calibration and initiation of hydrological models can improve flood forecasting.

The processing of number and gender agreement in Spanish: an event related potential investigation of the effects of structural distance

Previous research suggests that the processing of agreement is affected by the distance between the agreeing elements. However, the unique contribution of structural distance (number of intervening syntactic phrases) to the processing of agreement remains an open question, since previous investigations do not tease apart structural and linear distance (number of intervening words). We used event related potentials (ERPs) to examine the extent to which structural distance impacts the processing of Spanish number and gender agreement. Violations were realized both within the phrase and across the phrase. Across both levels of structural distance, linear distance was kept constant, as was the syntactic category of the agreeing elements. Number and gender agreement violations elicited a robust P600 between 400 and 900ms, a component associated with morphosyntactic processing. No amplitude differences were observed between number and gender violations, suggesting that the two features are processed similarly at the brain level. Within-phrase agreement yielded more positive waveforms than across-phrase agreement, both for agreement violations and for grammatical sentences (no agreement by distance interaction). These effects can be interpreted as evidence that structural distance impacts the establishment of agreement overall, consistent with sentence processing models which predict that hierarchical structure impacts the processing of syntactic dependencies. However, due to the lack of an agreement by distance interaction, the possibility cannot be ruled out that these effects are driven by differences in syntactic predictability between the within-phrase and across-phrase configurations, notably the fact that the syntactic category of the critical word was more predictable in the within-phrase conditions.

Influence of mass diffusion in sea ice dynamical models

The mixing of floes of different thickness caused by repeated deformation of the ice cover is modeled as diffusion, and the mass balance equation for sea ice accounting for mass diffusion is developed. The effect of deformational diffusion on the ice thickness balance is shown to reach 1% of the divergence effect, which describes ridging and lead formation. This means that with the same accuracy the mass balance equation can be written in terms of mean velocity rather than mean mass-weighted velocity, which one should correctly use for a multicomponent fluid such as sea ice with components identified by floe thickness. Mixing (diffusion) of sea ice also occurs because of turbulent variations in wind and ocean drags that are unresolved in models. Estimates of the importance of turbulent mass diffusion on the dynamic redistribution of ice thickness are determined using empirical data for the turbulent diffusivity. For long-time-scale prediction (≫5 days), where unresolved atmospheric motion may have a length scale on the order of the Arctic basin and the time scale is larger than the synoptic time scale of atmospheric events, turbulent mass diffusion can exceed 10% of the divergence effect. However, for short-time-scale prediction, for example, 5 days, the unresolved scales are on the order of 100 km, and turbulent diffusion is about 0.1% of the divergence effect. Because inertial effects are small in the dynamics of the sea ice pack, diffusive momentum transfer can be disregarded.

Impact of geographical region on urinary metabolomic and plasma fatty acid profiles in subjects with the metabolic syndrome across Europe: the LIPGENE study

The application of metabolomics in multi-centre studies is increasing. The aim of the present study was to assess the effects of geographical location on the metabolic profiles of individuals with the metabolic syndrome. Blood and urine samples were collected from 219 adults from seven European centres participating in the LIPGENE project (Diet, genomics and the metabolic syndrome: an integrated nutrition, agro-food, social and economic analysis). Nutrient intakes, BMI, waist:hip ratio, blood pressure, and plasma glucose, insulin and blood lipid levels were assessed. Plasma fatty acid levels and urine were assessed using a metabolomic technique. The separation of three European geographical groups (NW, northwest; NE, northeast; SW, southwest) was identified using partial least-squares discriminant analysis models for urine (R 2 X: 0•33, Q 2: 0•39) and plasma fatty acid (R 2 X: 0•32, Q 2: 0•60) data. The NW group was characterised by higher levels of urinary hippurate and N-methylnicotinate. The NE group was characterised by higher levels of urinary creatine and citrate and plasma EPA (20 : 5 n-3). The SW group was characterised by higher levels of urinary trimethylamine oxide and lower levels of plasma EPA. The indicators of metabolic health appeared to be consistent across the groups. The SW group had higher intakes of total fat and MUFA compared with both the NW and NE groups (P≤ 0•001). The NE group had higher intakes of fibre and n-3 and n-6 fatty acids compared with both the NW and SW groups (all P< 0•001). It is likely that differences in dietary intakes contributed to the separation of the three groups. Evaluation of geographical factors including diet should be considered in the interpretation of metabolomic data from multi-centre studies.

Ecosystem effects of CO2 concentration: evidence from past climates

Atmospheric CO2 concentration has varied from minima of 170-200 ppm in glacials to maxima of 280-300 ppm in the recent interglacials. Photosynthesis by C-3 plants is highly sensitive to CO2 concentration variations in this range. Physiological consequences of the CO2 changes should therefore be discernible in palaeodata. Several lines of evidence support this expectation. Reduced terrestrial carbon storage during glacials, indicated by the shift in stable isotope composition of dissolved inorganic carbon in the ocean, cannot be explained by climate or sea-level changes. It is however consistent with predictions of current process-based models that propagate known physiological CO2 effects into net primary production at the ecosystem scale. Restricted forest cover during glacial periods, indicated by pollen assemblages dominated by non-arboreal taxa, cannot be reproduced accurately by palaeoclimate models unless CO2 effects on C-3-C-4 plant competition are also modelled. It follows that methods to reconstruct climate from palaeodata should account for CO2 concentration changes. When they do so, they yield results more consistent with palaeoclimate models. In conclusion, the palaeorecord of the Late Quaternary, interpreted with the help of climate and ecosystem models, provides evidence that CO2 effects at the ecosystem scale are neither trivial nor transient.

PERSiST: a flexible rainfall-runoff modelling toolkit for use with the INCA family of models

Runoff generation processes and pathways vary widely between catchments. Credible simulations of solute and pollutant transport in surface waters are dependent on models which facilitate appropriate, catchment-specific representations of perceptual models of the runoff generation process. Here, we present a flexible, semi-distributed landscape-scale rainfall-runoff modelling toolkit suitable for simulating a broad range of user-specified perceptual models of runoff generation and stream flow occurring in different climatic regions and landscape types. PERSiST (the Precipitation, Evapotranspiration and Runoff Simulator for Solute Transport) is designed for simulating present-day hydrology; projecting possible future effects of climate or land use change on runoff and catchment water storage; and generating hydrologic inputs for the Integrated Catchments (INCA) family of models. PERSiST has limited data requirements and is calibrated using observed time series of precipitation, air temperature and runoff at one or more points in a river network. Here, we apply PERSiST to the river Thames in the UK and describe a Monte Carlo tool for model calibration, sensitivity and uncertainty analysis

In vitro and in vivo models of colorectal cancer: antigenotoxic activity of berries.

The etiology of colorectal cancer (CRC), a common cause of cancer-related mortality globally, has strong associations with diet. There is considerable epidemiological evidence that fruits and vegetables are associated with reduced risk of CRC. This paper reviews the extensive evidence, both from in vitro studies and animal models, that components of berry fruits can modulate biomarkers of DNA damage and that these effects may be potentially chemoprotective, given the likely role that oxidative damage plays in mutation rate and cancer risk. Human intervention trials with berries are generally consistent in indicating a capacity to significantly decrease oxidative damage to DNA, but represent limited evidence for anticarcinogenicity, relying as they do on surrogate risk markers. To understand the effects of berry consumption on colorectal cancer risk, future studies will need to be well controlled, with defined berry extracts, using suitable and clinically relevant end points and considering the importance of the gut microbiota.