Local and average structure in zinc cyanide: towards an understanding of the atomistic origin of negative thermal expansion

Neutron diffraction at 11.4 and 295 K and solid-state 67Zn NMR are used to determine both the local and average structures in the disordered, negative thermal expansion (NTE) material, Zn(CN)2. Solid-state NMR not only confirms that there is head-to-tail disorder of the C≡N groups present in the solid, but yields information about the relative abundances of the different Zn(CN)4-n(NC)n tetrahedral species, which do not follow a simple binomial distribution. The Zn(CN)4 and Zn(NC)4 species occur with much lower probabilities than are predicted by binomial theory, supporting the conclusion that they are of higher energy than the other local arrangements. The lowest energy arrangement is Zn(CN)2(NC)2. The use of total neutron diffraction at 11.4 K, with analysis of both the Bragg diffraction and the derived total correlation function, yields the first experimental determination of the individual Zn−N and Zn−C bond lengths as 1.969(2) and 2.030(2) Å, respectively. The very small difference in bond lengths, of ~0.06 Å, means that it is impossible to obtain these bond lengths using Bragg diffraction in isolation. Total neutron diffraction also provides information on both the average and local atomic displacements responsible for NTE in Zn(CN)2. The principal motions giving rise to NTE are shown to be those in which the carbon and nitrogen atoms within individual Zn−C≡N−Zn linkages are displaced to the same side of the Zn···Zn axis. Displacements of the carbon and nitrogen atoms to opposite sides of the Zn···Zn axis, suggested previously in X-ray studies as being responsible for NTE behavior, in fact make negligible contribution at temperatures up to 295 K.

Variation among Attic fine wares: the case of the Pan Painter's pelikai

This paper is a case study of the continuum between standardization and variation in the production of red-figure Athenian fine wares in the first half of the 5th century BC. An investigation of the Pan Painter's pelikai reveals that they fall into 3 distinct groups, according to size. While the pelikai in each group are also distinguishable from each other by shape, pattern, and iconography, the next clearest distinction between the groups (after size) is in their style of decoration. The pelikai in the largest group, which is comprised of small pelikai, are particularly distinct from the Pan Painter's broader oeuvre of ca. 220 vases insofar as they exemplify a lackadaisical painting style, which I have termed banausic, on account of its frequent use for images of craftsmen, women at work, and other such genre images. While this casual style is antithetical to the Pain Painter's refined style, for which he is better known, and which he employs for his large pelikai, affinities between the 2 styles—as judged by his confident line, anatomical details, and other technical features—permit the conclusion that this group of pelikai were executed by one and the same craftsman as the others. As with all of the vases attributed to this talented painter, however, the pelikai—whether large or small—are decorated with a great bariety of images. While most painted Athenian vases are understood to have been individually created, not mass-produced, the Pan Painter's coherent group of small pelikai seem to have been created en masse, in a uniform size and shape and with a distinct decorative style. This group of standardized vases represents a body of work executed under the influence or at the behest of a specific vase workshop. The form of the small pelikai in fact allows us to associate them with the Geras Painter. With his work on these small pelikai, perhaps in the latter part of his career, the Pan Painter may have intentionally minimized variability in favour of standardization, to meet market demands.

Structure and stress of Re(11%21); chiral terraces at a racemic surface

The surface structure and morphology of the clean Re(11%21) surface has been investigated through combined low energy electron diffraction intensity analysis of data taken at multiple angles of incidence, scanning tunneling microscopy, and first-principles density functional calculations. The results show how this globally racemic surface terminates in two chirally distinct terraces, which show largescale out-of-plane atomic relaxations and in-plane lateral movement of the uppermost atoms. We further identify and discuss the initial stages of step bunching upon adsorption of oxygen that leads ultimately to the large-scale faceting of the surface. Finally, we present calculations of surface stress and the response to applied surface strain, which suggest routes to the exertion of control over the expression of chirality at the surface.

Postpartum GAD is a risk factor for postpartum MDD: the course and longitudinal relationships of postpartum GAD and MDD

Background The objective was to examine the course and longitudinal associations of generalized anxiety disorder (GAD) and major depressive disorder (MDD) in mothers over the postpartum 2 years. Method Using a prospective naturalistic design, 296 mothers recruited from a large community pool were assessed for GAD and MDD at 3, 6, 10, 14, and 24 months postpartum. Structured clinical interviews were used for diagnoses, and symptoms were assessed using self-report questionnaires. Logistic regression analyses were used to examine diagnostic stability and longitudinal relations, and latent variable modeling was employed to examine change in symptoms. Results MDD without co-occurring GAD, GAD without co-occurring MDD, and co-occurring GAD and MDD, displayed significant stability during the postpartum period. Whereas MDD did not predict subsequent GAD, GAD predicted subsequent MDD (in the form of GAD + MDD). Those with GAD + MDD at 3 months postpartum were significantly less likely to be diagnosis free during the follow-up period than those in other diagnostic categories. At the symptom level, symptoms of GAD were more trait-like than those of depression. Conclusions Postpartum GAD and MDD are relatively stable conditions, and GAD is a risk factor for MDD but not vice versa. Given the tendency of MDD and GAD to be persistent, especially when comorbid, and the increased risk for MDD in mothers with GAD, as well as the potential negative effects of cumulative exposure to maternal depression and anxiety on child development, the present findings clearly highlight the need for screening and treatment of GAD in addition to MDD during the postpartum period.

Species distribution models for crop pollination: a modelling framework applied to Great Britain

Insect pollination benefits over three quarters of the world's major crops. There is growing concern that observed declines in pollinators may impact on production and revenues from animal pollinated crops. Knowing the distribution of pollinators is therefore crucial for estimating their availability to pollinate crops; however, in general, we have an incomplete knowledge of where these pollinators occur. We propose a method to predict geographical patterns of pollination service to crops, novel in two elements: the use of pollinator records rather than expert knowledge to predict pollinator occurrence, and the inclusion of the managed pollinator supply. We integrated a maximum entropy species distribution model (SDM) with an existing pollination service model (PSM) to derive the availability of pollinators for crop pollination. We used nation-wide records of wild and managed pollinators (honey bees) as well as agricultural data from Great Britain. We first calibrated the SDM on a representative sample of bee and hoverfly crop pollinator species, evaluating the effects of different settings on model performance and on its capacity to identify the most important predictors. The importance of the different predictors was better resolved by SDM derived from simpler functions, with consistent results for bees and hoverflies. We then used the species distributions from the calibrated model to predict pollination service of wild and managed pollinators, using field beans as a test case. The PSM allowed us to spatially characterize the contribution of wild and managed pollinators and also identify areas potentially vulnerable to low pollination service provision, which can help direct local scale interventions. This approach can be extended to investigate geographical mismatches between crop pollination demand and the availability of pollinators, resulting from environmental change or policy scenarios.

Infrared optical coatings for the EarthCARE Multispectral Imager

The Earth Cloud, Aerosol and Radiation Explorer mission (EarthCARE) Multispectral Imager (MSI) is a radiometric instrument designed to provide the imaging of the atmospheric cloud cover and the cloud top surface temperature from a sun-synchronous low Earth orbit. The MSI forms part of a suite of four instruments destined to support the European Space Agency Living Planet mission on-board the EarthCARE satellite payload to be launched in 2016, whose synergy will be used to construct three-dimensional scenes, textures and temperatures of atmospheric clouds and aerosols. The MSI instrument contains seven channels: four solar channels to measure visible and short-wave infrared wavelengths, and three channels to measure infrared thermal emission. In this paper, we describe the optical layout of the infrared instrument channels, thin-film multilayer designs, the coating deposition method and the spectral system throughput for the bandpass interference filters, dichroic beam splitters, lenses and mirror coatings to discriminate wavelengths at 8.8, 10.8, & 12.0 µm. The rationale for the selection of thin-film materials, spectral measurement technique, and environmental testing performance are also presented.

Parent-reported gastro-intestinal symptoms in children with autism spectrum disorders

The objective of this study is to investigate whether parentally-reported gastro-intestinal (GI) symptoms are increased in a population-derived sample of children with autism spectrum disorders (ASD) compared to controls. Participants included 132 children with ASD and 81 with special educational needs (SEN) but no ASD, aged 10-14 years plus 82 typically developing (TD) children. Data were collected on GI symptoms, diet, cognitive abilities, and developmental histories. Nearly half (weighted rate 46.5 %) of children with ASD had at least one individual lifetime GI symptom compared with 21.8 % of TD children and 29.2 % of those with SEN. Children with ASD had more past and current GI symptoms than TD or SEN groups although fewer current symptoms were reported in all groups compared with the past. The ASD group had significantly increased past vomiting and diarrhoea compared with the TD group and more abdominal pain than the SEN group. The ASD group had more current constipation (when defined as bowel movement less than three times per week) and soiling than either the TD or SEN groups. No association was found between GI symptoms and intellectual ability, ASD severity, ASD regression or limited or faddy diet. Parents report more GI symptoms in children with ASD than children with either SEN or TD children but the frequency of reported symptoms is greater in the past than currently in all groups.

Flux transfer events at the dayside magnetopause: transient reconnection or magnetosheath dynamic pressure pulses?

The suggestion is discussed that characteristic particle and field signatures at the dayside magnetopause, termed “flux transfer events” (FTEs), are, in at least some cases, due to transient solar wind and/or magnetosheath dynamic pressure increases, rather than time-dependent magnetic reconnection. It is found that most individual cases of FTEs observed by a single spacecraft can, at least qualitatively, be explained by the pressure pulse model, provided a few rather unsatisfactory features of the predictions are explained in terms of measurement uncertainties. The most notable exceptions to this are some “two-regime” observations made by two satellites simultaneously, one on either side of the magnetopause. However, this configuration has not been frequently achieved for sufficient time, such observations are rare, and the relevant tests are still not conclusive. The strongest evidence that FTEs are produced by magnetic reconnection is the dependence of their occurrence on the north-south component of the interplanetary magnetic field (IMF) or of the magnetosheath field. The pressure pulse model provides an explanation for this dependence (albeit qualitative) in the case of magnetosheath FTEs, but this does not apply to magnetosphere FTEs. The only surveys of magnetosphere FTEs have not employed the simultaneous IMF, but have shown that their occurrence is strongly dependent on the north-south component of the magnetosheath field, as observed earlier/later on the same magnetopause crossing (for inbound/outbound passes, respectively). This paper employs statistics on the variability of the IMF orientation to investigate the effects of IMF changes between the times of the magnetosheath and FTE observations. It is shown that the previously published results are consistent with magnetospheric FTEs being entirely absent when the magnetosheath field is northward: all crossings with magnetosphere FTEs and a northward field can be attributed to the field changing sense while the satellite was within the magnetosphere (but close enough to the magnetopause to detect an FTE). Allowance for the IMF variability also makes the occurrence frequency of magnetosphere FTEs during southward magnetosheath fields very similar to that observed for magnetosheath FTEs. Conversely, the probability of attaining the observed occurrence frequencies for the pressure pulse model is 10−14. In addition, it is argued that some magnetosheath FTEs should, for the pressure pulse model, have been observed for northward IMF: the probability that the number is as low as actually observed is estimated to be 10−10. It is concluded that although the pressure model can be invoked to qualitatively explain a large number of individual FTE observations, the observed occurrence statistics are in gross disagreement with this model.

Enhanced Australian carbon sink despite increased wildfire during the 21st century

Climate projections show Australia becoming significantly warmer during the 21st century, and precipitation decreasing over much of the continent. Such changes are conventionally considered to increase wildfire risk. Nevertheless, we show that burnt area increases in southern Australia, but decreases in northern Australia. Overall the projected increase in fire is small (0.72–1.31% of land area, depending on the climate scenario used), and does not cause a decrease in carbon storage. In fact, carbon storage increases by 3.7–5.6 Pg C (depending on the climate scenario used). Using a process-based model of vegetation dynamics, vegetation–fire interactions and carbon cycling, we show increased fire promotes a shift to more fire-adapted trees in wooded areas and their encroachment into grasslands, with an overall increase in forested area of 3.9–11.9%. Both changes increase carbon uptake and storage. The increase in woody vegetation increases the amount of coarse litter, which decays more slowly than fine litter hence leading to a relative reduction in overall heterotrophic respiration, further reducing carbon losses. Direct CO2 effects increase woody cover, water-use efficiency and productivity, such that carbon storage is increased by 8.5–14.8 Pg C compared to simulations in which CO2 is held constant at modern values. CO2 effects tend to increase burnt area, fire fluxes and therefore carbon losses in arid areas, but increase vegetation density and reduce burnt area in wooded areas.

What is outside? The early years foundation stage in England: outdoor facilities, organisation and staff attitudes

The purpose of this paper is to report on the facilities available, organisation of, and staff attitudes to early years outdoor education from schools within the south east of England, focusing on provision for children aged three to five. One component of the successful education of the child involves providing an ‘environment for learning’, including the facilities, layout and routines. This paper presents findings concerning the type and variety of facilities available outside; the various styles of organisation of the space; staff attitudes about: their roles, their aims for the environment, children’s behaviour and learning, and perceived drawbacks to practice. This paper draws on empirical data collected from schools within the University of Reading partnership. The findings suggest that although all early years settings must adhere to the statutory framework there are a range of facilities available, and there are a number of ways this environment is organised. Further there appears to be uncertainty about the adult role outside and the aims for activities. The conclusions drawn indicate that staff do not appear to be linking their aims for outdoor education to the facilities provided or to their actions outside. This means there is not a clear link between what staff provide outside and the declared ambitions for learning. This study is important as all educators need to be certain about their aims for education to ensure best outcomes for children. The implications of these findings for early years teachers are that they need to be able to articulate their aims for outdoor education and to provide the correct facilities to achieve these aims. Finally this study was undertaken to raise debate, posit questions and to ascertain the parameters for further research about the early years outdoor environment.

The dependence of wintertime Mediterranean precipitation on the atmospheric circulation response to climate change

Climate models indicate a future wintertime precipitation reduction in the Mediterranean region but there is large uncertainty in the amplitude of the projected change. We analyse CMIP5 climate model output to quantify the role of atmospheric circulation in the Mediterranean precipitation change. It is found that a simple circulation index, i.e. the 850 hPa zonal wind (U850) in North Africa, well describes the year to year fluctuations in the area-averaged Mediterranean precipitation, with positive (i.e. westerly) U850 anomalies in North Africa being associated with positive precipitation anomalies. Under climate change, U850 in North Africa and the Mediterranean precipitation are both projected to decrease consistently with the relationship found in the inter-annual variability. This enables us to estimate that about 85% of the CMIP5 mean precipitation response and 80% of the variance in the inter-model spread are related to changes in the atmospheric circulation. In contrast, there is no significant correlation between the mean precipitation response and the global-mean surface warming across the models. It follows that the uncertainty in cold-season Mediterranean precipitation projection will not be narrowed unless the uncertainty in the atmospheric circulation response is reduced.

Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.

Effects of a web-based personalized intervention on physical activity in European adults: a randomized controlled trial

Background: The high prevalence of physical inactivity worldwide calls for innovative and more effective ways to promote physical activity (PA). There are limited objective data on the effectiveness of Web-based personalized feedback on increasing PA in adults. Objective: It is hypothesized that providing personalized advice based on PA measured objectively alongside diet, phenotype, or genotype information would lead to larger and more sustained changes in PA, compared with nonpersonalized advice. Methods: A total of 1607 adults in seven European countries were randomized to either a control group (nonpersonalized advice, Level 0, L0) or to one of three personalized groups receiving personalized advice via the Internet based on current PA plus diet (Level 1, L1), PA plus diet and phenotype (Level 2, L2), or PA plus diet, phenotype, and genotype (Level 3, L3). PA was measured for 6 months using triaxial accelerometers, and self-reported using the Baecke questionnaire. Outcomes were objective and self-reported PA after 3 and 6 months. Results: While 1270 participants (85.81% of 1480 actual starters) completed the 6-month trial, 1233 (83.31%) self-reported PA at both baseline and month 6, but only 730 (49.32%) had sufficient objective PA data at both time points. For the total cohort after 6 months, a greater improvement in self-reported total PA (P=.02) and PA during leisure (nonsport) (P=.03) was observed in personalized groups compared with the control group. For individuals advised to increase PA, we also observed greater improvements in those two self-reported indices (P=.006 and P=.008, respectively) with increased personalization of the advice (L2 and L3 vs L1). However, there were no significant differences in accelerometer results between personalized and control groups, and no significant effect of adding phenotypic or genotypic information to the tailored feedback at month 3 or 6. After 6 months, there were small but significant improvements in the objectively measured physical activity level (P<.05), moderate PA (P<.01), and sedentary time (P<.001) for individuals advised to increase PA, but these changes were similar across all groups. Conclusions: Different levels of personalization produced similar small changes in objective PA. We found no evidence that personalized advice is more effective than conventional “one size fits all” guidelines to promote changes in PA in our Web-based intervention when PA was measured objectively. Based on self-reports, PA increased to a greater extent with more personalized advice. Thus, it is crucial to measure PA objectively in any PA intervention study.

Fairtrade movement

An outline is provided of how the fair trade movement has developed and its success in stimulating the production, circulation and consumption of fair trade products. Critical debate over the core message of the fair trade movement, that buying fair trade products can transform producers’ lives in the global south, is highlighted. A body of ethnographic research contributes to this debate by examining the significance of fair trade in producers’ lives.

The curious case of the camelthorn: competition, coexistence and nest-site limitation in a multispecies mutualism

Myrmecophyte plants house ants in domatia in exchange for protection from herbivores. Ant-myrmecophyte mutualisms exhibit two general patterns due to competition between ants for plant occupancy: i) domatia nest-sites are a limiting resource and ii) each individual plant hosts one ant species at a time. However, individual camelthorn trees (Vachellia erioloba) typically host two to four ant species simultaneously, often coexisting in adjacent domatia on the same branch. Such fine-grain spatial coexistence brings into question the conventional wisdom on ant-myrmecophyte mutualisms. Camelthorn ants appear not to be nest-site limited, despite low abundance of suitable domatia, and have random distributions of nest-sites within and across trees. These patterns suggest a lack of competition between ants for domatia and contrast strongly with other ant-myrmecophyte systems. Comparison of this unusual case with others suggests that spatial scale is crucial to coexistence or competitive exclusion involving multiple ant species. Furthermore, coexistence may be facilitated when co-occurring ant species diverge strongly on at least one niche axis. Our conclusions provide recommendations for future ant-myrmecophyte research, particularly in utilising multispecies systems to further our understanding of mutualism biology.