Spin-canted antiferromagnetic phase transitions in alternating phenoxo- and carboxylato-bridged Mn(III)-salen complexes

Three new MnIII complexes, {[Mn-2(salen)(2)(OCn)](ClO4)}(n) (1), {[Mn-2(salen)(2)(OPh)](ClO4)}(n) (2) and {[Mn-2(salen)(2)(OBz)](ClO4)}(2) (3) (where salen = N,N'-bis(salicylidene)-1,2-diaminoethane dianion, OCn = cinnamate, OPh = phenylacetate and OBz = benzoate), have been synthesized and characterized structurally and magnetically. The crystal structures reveal that all three structures contain syn-anti carboxylatebridged dimeric [Mn-2(salen)(2)(OOCR)](+) cations (OOCR = bridging carboxylate) that are joined together by weak Mn center dot center dot center dot O(phenoxo) interactions to form infinite alternating chain structures in 1 and 2, but the relatively long Mn center dot center dot center dot O(phenoxo) distance [3.621(2)angstrom] in 3 restricts this structure to tetranuclear units. Magnetic studies showed that 1 and 2 exhibited magnetic long-range order at T-N = 4.0 and 4.6 K (T-N = Neel transition temperature), respectively, to give spin-canted antiferromagnetic structures. Antiferromagnetic coupling was also observed in 3 but no peaks were recorded in the field-cooled magnetization (FCM) or zero-field-cooled magnetization (ZFCM) data, indicating that 3 remained paramagnetic down to 2 K. This dominant antiferromagnetic coupling is attributed to the carboxylate bridges. The ferromagnetic coupling expected due to the Mn-O(phenoxo)center dot center dot center dot Mn bridge plays an auxiliary role in the magnetic chain, but is an essential component of the bulk magnetic properties of the material.

Reframing 'crisis' in fair trade coffee production: trajectories of agrarian change in Nicaragua

A focus on crisis provides a methodological window to understand how agrarian change shapes producer engagement in fair trade. This orientation challenges a seperation between the market and development, situating fair trade within global processes that incorporate agrarian histories of social change and conflict. Reframing crisis as a condition of agrarian life, rather than emphasizing its cyclical manifestation within the global economy, reveals how market-driven development encompasses the material conditions of peoples' existence in ambiguous and contradictory ways. Drawing on the case of coffee production in Nicaragua, experiences of crisis demonstrate that greater attention needs to be paid to the socioeconomic and political dimensions of development within regional commodity assemblages to address entrenched power relations and unequal access to land and resources. This questions moral certainties when examining the paradox of working in and against the market, and suggests that a better understanding of specific trajectories of development could improve fair trade's objective of enhancing producer livelihoods.

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.

Impact of stratospheric ozone on Southern Hemisphere circulation change: A multimodel assessment

The impact of stratospheric ozone on the tropospheric general circulation of the Southern Hemisphere (SH) is examined with a set of chemistry‐climate models participating in the Stratospheric Processes and their Role in Climate (SPARC)/Chemistry‐Climate Model Validation project phase 2 (CCMVal‐2). Model integrations of both the past and future climates reveal the crucial role of stratospheric ozone in driving SH circulation change: stronger ozone depletion in late spring generally leads to greater poleward displacement and intensification of the tropospheric midlatitude jet, and greater expansion of the SH Hadley cell in the summer. These circulation changes are systematic as poleward displacement of the jet is typically accompanied by intensification of the jet and expansion of the Hadley cell. Overall results are compared with coupled models participating in the Intergovernmental Panel on Climate Change Fourth Assessment Report (IPCC AR4), and possible mechanisms are discussed. While the tropospheric circulation response appears quasi‐linearly related to stratospheric ozone changes, the quantitative response to a given forcing varies considerably from one model to another. This scatter partly results from differences in model climatology. It is shown that poleward intensification of the westerly jet is generally stronger in models whose climatological jet is biased toward lower latitudes. This result is discussed in the context of quasi‐geostrophic zonal mean dynamics.

The impacts of climate change on river flow regimes at the global scale

This paper presents an assessment of the impacts of climate change on a series of indicators of hydrological regimes across the global domain, using a global hydrological model run with climate scenarios constructed using pattern-scaling from 21 CMIP3 (Coupled Model Intercomparison Project Phase 3) climate models. Changes are compared with natural variability, with a significant change being defined as greater than the standard deviation of the hydrological indicator in the absence of climate change. Under an SRES (Special Report on Emissions Scenarios) A1b emissions scenario, substantial proportions of the land surface (excluding Greenland and Antarctica) would experience significant changes in hydrological behaviour by 2050; under one climate model scenario (Hadley Centre HadCM3), average annual runoff increases significantly over 47% of the land surface and decreases over 36%; only 17% therefore sees no significant change. There is considerable variability between regions, depending largely on projected changes in precipitation. Uncertainty in projected river flow regimes is dominated by variation in the spatial patterns of climate change between climate models (hydrological model uncertainty is not included). There is, however, a strong degree of consistency in the overall magnitude and direction of change. More than two-thirds of climate models project a significant increase in average annual runoff across almost a quarter of the land surface, and a significant decrease over 14%, with considerably higher degrees of consistency in some regions. Most climate models project increases in runoff in Canada and high-latitude eastern Europe and Siberia, and decreases in runoff in central Europe, around the Mediterranean, the Mashriq, central America and Brasil. There is some evidence that projecte change in runoff at the regional scale is not linear with change in global average temperature change. The effects of uncertainty in the rate of future emissions is relatively small

Private climate change reporting: an emerging discourse of risk and opportunity?

Purpose – This paper aims to explore the nature of the emerging discourse of private climate change reporting, which takes place in one-on-one meetings between institutional investors and their investee companies. Design/methodology/approach – Semi-structured interviews were conducted with representatives from 20 UK investment institutions to derive data which was then coded and analysed, in order to derive a picture of the emerging discourse of private climate change reporting, using an interpretive methodological approach, in addition to explorative analysis using NVivo software. Findings – The authors find that private climate change reporting is dominated by a discourse of risk and risk management. This emerging risk discourse derives from institutional investors' belief that climate change represents a material risk, that it is the most salient sustainability issue, and that their clients require them to manage climate change-related risk within their portfolio investment. It is found that institutional investors are using the private reporting process to compensate for the acknowledged inadequacies of public climate change reporting. Contrary to evidence indicating corporate capture of public sustainability reporting, these findings suggest that the emerging private climate change reporting discourse is being captured by the institutional investment community. There is also evidence of an emerging discourse of opportunity in private climate change reporting as the institutional investors are increasingly aware of a range of ways in which climate change presents material opportunities for their investee companies to exploit. Lastly, the authors find an absence of any ethical discourse, such that private climate change reporting reinforces rather than challenges the “business case” status quo. Originality/value – Although there is a wealth of sustainability reporting research, there is no academic research on private climate change reporting. This paper attempts to fill this gap by providing rich interview evidence regarding the nature of the emerging private climate change reporting discourse.

Private climate change reporting: a discourse of risk and opportunity

Purpose – This paper aims to explore the nature of the emerging discourse of private climate change reporting, which takes place in one-on-one meetings between institutional investors and their investee companies. Design/methodology/approach – Semi-structured interviews were conducted with representatives from 20 UK investment institutions to derive data which was then coded and analysed, in order to derive a picture of the emerging discourse of private climate change reporting, using an interpretive methodological approach, in addition to explorative analysis using NVivo software. Findings – The authors find that private climate change reporting is dominated by a discourse of risk and risk management. This emerging risk discourse derives from institutional investors' belief that climate change represents a material risk, that it is the most salient sustainability issue, and that their clients require them to manage climate change-related risk within their portfolio investment. It is found that institutional investors are using the private reporting process to compensate for the acknowledged inadequacies of public climate change reporting. Contrary to evidence indicating corporate capture of public sustainability reporting, these findings suggest that the emerging private climate change reporting discourse is being captured by the institutional investment community. There is also evidence of an emerging discourse of opportunity in private climate change reporting as the institutional investors are increasingly aware of a range of ways in which climate change presents material opportunities for their investee companies to exploit. Lastly, the authors find an absence of any ethical discourse, such that private climate change reporting reinforces rather than challenges the “business case” status quo. Originality/value – Although there is a wealth of sustainability reporting research, there is no academic research on private climate change reporting. This paper attempts to fill this gap by providing rich interview evidence regarding the nature of the emerging private climate change reporting discourse.

Measuring large topographic change with InSAR: lava thicknesses, extrusion rate and subsidence rate at Santiaguito volcano, Guatemala

Lava flows can produce changes in topography on the order of 10s-100s of metres. A knowledge of the resulting volume change provides evidence about the dynamics of an eruption. We present a method to measure topographic changes from the differential InSAR phase delays caused by the height differences between the current topography and a Digital Elevation Model (DEM). This does not require a pre-event SAR image, so it does not rely on interferometric phase remaining coherent during eruption and emplacement. Synthetic tests predicts that we can estimate lava thickness of as little as �9 m, given a minimum of 5 interferograms with suitably large orbital baseine separations. In the case of continuous motion, such as lava flow subsidence, we invert interferometric phase simultaneously for topographic change and displacement. We demonstrate the method using data from Santiaguito volcano, Guatemala, and measure increases in lava thickness of up to 140 m between 2000 and 2009, largely associated with activity between 2000 and 2005. We find a mean extrusion rate of 0.43 +/- 0.06 m3/s, which lies within the error bounds of the longer term extrusion rate between 1922-2000. The thickest and youngest parts of the flow deposit were shown to be subsiding at an average rate of �-6 cm/yr. This is the first time that flow thickness and subsidence have been measured simultaneously. We expect this method to be suitable for measurment of landslides and other mass flow deposits as well as lava flows.

Simple uncertainty frameworks for selecting weighting schemes and interpreting multimodel ensemble climate change experiments

Future climate change projections are often derived from ensembles of simulations from multiple global circulation models using heuristic weighting schemes. This study provides a more rigorous justification for this by introducing a nested family of three simple analysis of variance frameworks. Statistical frameworks are essential in order to quantify the uncertainty associated with the estimate of the mean climate change response. The most general framework yields the “one model, one vote” weighting scheme often used in climate projection. However, a simpler additive framework is found to be preferable when the climate change response is not strongly model dependent. In such situations, the weighted multimodel mean may be interpreted as an estimate of the actual climate response, even in the presence of shared model biases. Statistical significance tests are derived to choose the most appropriate framework for specific multimodel ensemble data. The framework assumptions are explicit and can be checked using simple tests and graphical techniques. The frameworks can be used to test for evidence of nonzero climate response and to construct confidence intervals for the size of the response. The methodology is illustrated by application to North Atlantic storm track data from the Coupled Model Intercomparison Project phase 5 (CMIP5) multimodel ensemble. Despite large variations in the historical storm tracks, the cyclone frequency climate change response is not found to be model dependent over most of the region. This gives high confidence in the response estimates. Statistically significant decreases in cyclone frequency are found on the flanks of the North Atlantic storm track and in the Mediterranean basin.

Choice-induced preference change in the free-choice paradigm: a critical methodological review

Choices not only reflect our preference, but they also affect our behavior. The phenomenon of choice-induced preference change has been of interest to cognitive dissonance researchers in social psychology, and more recently, it has attracted the attention of researchers in economics and neuroscience. Preference modulation after the mere act of making a choice has been repeatedly demonstrated over the last 50 years by an experimental paradigm called the “free-choice paradigm.” However, Chen and Risen (2010) pointed out a serious methodological flaw in this paradigm, arguing that evidence for choice-induced preference change is still insufficient. Despite the flaw, studies using the traditional free-choice paradigm continue to be published without addressing the criticism. Here, aiming to draw more attention to this issue, we briefly explain the methodological problem, and then describe simple simulation studies that illustrate how the free-choice paradigm produces a systematic pattern of preference change consistent with cognitive dissonance, even without any change in true preference. Our stimulation also shows how a different level of noise in each phase of the free-choice paradigm independently contributes to the magnitude of artificial preference change. Furthermore, we review ways of addressing the critique and provide a meta-analysis to show the effect size of choice-induced preference change after addressing the critique. Finally, we review and discuss, based on the results of the stimulation studies, how the criticism affects our interpretation of past findings generated from the free-choice paradigm. We conclude that the use of the conventional free-choice paradigm should be avoided in future research and the validity of past findings from studies using this paradigm should be empirically re-established. (PsycINFO Database Record (c) 2013 APA, all rights reserved)(journal abstract)

Success and failure of grassroots innovations for addressing climate change: the case of the Transition Movement

Grassroots innovations emerge as networks generating innovative solutions for climate change adaptation and mitigation. However, it is unclear if grassroots innovations can be successful in responding to climate change. Little evidence exists on replication, international comparisons are rare, and research tends to overlook discontinued responses in favour of successful ones. We take the Transition Movement as a case study of a rapidly spreading transnational grassroots network, and include both active and non-active local transition initiatives. We investigate the replication of grassroots innovations in different contexts with the aim to uncover general patterns of success and failure, and identify questions for future research. An online survey was carried out in 23 countries (N=276). The data analysis entailed testing the effect of internal and contextual factors of success as drawn from the existing literature, and the identification of clusters of transition initiatives with similar internal and contextual factor configurations. Most transition initiatives consider themselves successful. Success is defined along the lines of social connectivity and empowerment, and external environmental impact. We find that less successful transition initiatives might underestimate the importance of contextual factors and material resources in influencing success. We also find that their diffusion is linked to the combination of local-global learning processes, and that there is an incubation period during which a transition initiative is consolidated. Transition initiatives seem capable of generalising organisational principles derived from unique local experiences that seem to be effective in other local contexts. However, the geographical locations matter with regard to where transition initiatives take root and the extent of their success, and ‘place attachment’ may have a role in the diffusion of successful initatives. We suggest that longitudinal comparative studies can advance our understanding in this regard, as well as inform the changing nature of the definition of success at different stages of grassroots innovation development, and the dynamic nature of local and global linkages.

Northern winter climate change: assessment of uncertainty in CMIP5 projections related to stratosphere–troposphere coupling

Future changes in the stratospheric circulation could have an important impact on Northern winter tropospheric climate change, given that sea level pressure (SLP) responds not only to tropospheric circulation variations but also to vertically coherent variations in troposphere-stratosphere circulation. Here we assess Northern winter stratospheric change and its potential to influence surface climate change in the Coupled Model Intercomparison Project – phase 5 (CMIP5) multi-model ensemble. In the stratosphere at high latitudes, an easterly change in zonally averaged zonal wind is found for the majority of the CMIP5 models, under the Representative Concentration Pathway 8.5 scenario. Comparable results are also found in the 1% CO2 increase per year projections, indicating that the stratospheric easterly change is common feature in future climate projections. This stratospheric wind change, however, shows a significant spread among the models. By using linear regression, we quantify the impact of tropical upper troposphere warming, polar amplification and the stratospheric wind change on SLP. We find that the inter-model spread in stratospheric wind change contributes substantially to the inter-model spread in Arctic SLP change. The role of the stratosphere in determining part of the spread in SLP change is supported by the fact that the SLP change lags the stratospheric zonally averaged wind change. Taken together, these findings provide further support for the importance of simulating the coupling between the stratosphere and the troposphere, to narrow the uncertainty in the future projection of tropospheric circulation changes.

Categorizing users in behavior change support systems based on cognitive dissonance

Most developers of behavior change support systems (BCSS) employ ad hoc procedures in their designs. This paper presents a novel discussion concerning how analyzing the relationship between attitude toward target behavior, current behavior, and attitude toward change or maintaining behavior can facilitate the design of BCSS. We describe the three-dimensional relationships between attitude and behavior (3D-RAB) model and demonstrate how it can be used to categorize users, based on variations in levels of cognitive dissonance. The proposed model seeks to provide a method for analyzing the user context on the persuasive systems design model, and it is evaluated using existing BCSS. We identified that although designers seem to address the various cognitive states, this is not done purposefully, or in a methodical fashion, which implies that many existing applications are targeting users not considered at the design phase. As a result of this work, it is suggested that designers apply the 3D-RAB model in order to design solutions for targeted users.

Attribution of the spatial pattern of CO2-forced sea level change to ocean surface flux changes

Climate models taking part in the coupled model intercomparison project phase 5 (CMIP5) all predict a global mean sea level rise for the 21st century. Yet the sea level change is not spatially uniform and differs among models. Here we evaluate the role of air–sea fluxes of heat, water and momentum (windstress) to find the spatial pattern associated to each of them as well as the spread they can account for. Using one AOGCM to which we apply the surface flux changes from other AOGCMs, we show that the heat flux and windstress changes dominate both the pattern and the spread, but taking the freshwater flux into account as well yields a sea level change pattern in better agreement with the CMIP5 ensemble mean. Differences among the CMIP5 control ocean temperature fields have a smaller impact on the sea level change pattern.

The dependence of radiative forcing and feedback on evolving patterns of surface temperature change in climate models

Experiments with CO2 instantaneously quadrupled and then held constant are used to show that the relationship between the global-mean net heat input to the climate system and the global-mean surface-air-temperature change is nonlinear in Coupled Model Intercomparison Project phase 5 (CMIP5) Atmosphere-Ocean General Circulation Models (AOGCMs). The nonlinearity is shown to arise from a change in strength of climate feedbacks driven by an evolving pattern of surface warming. In 23 out of the 27 AOGCMs examined the climate feedback parameter becomes significantly (95% confidence) less negative – i.e. the effective climate sensitivity increases – as time passes. Cloud feedback parameters show the largest changes. In the AOGCM-mean approximately 60% of the change in feedback parameter comes from the topics (30N-30S). An important region involved is the tropical Pacific where the surface warming intensifies in the east after a few decades. The dependence of climate feedbacks on an evolving pattern of surface warming is confirmed using the HadGEM2 and HadCM3 atmosphere GCMs (AGCMs). With monthly evolving sea-surface-temperatures and sea-ice prescribed from its AOGCM counterpart each AGCM reproduces the time-varying feedbacks, but when a fixed pattern of warming is prescribed the radiative response is linear with global temperature change or nearly so. We also demonstrate that the regression and fixed-SST methods for evaluating effective radiative forcing are in principle different, because rapid SST adjustment when CO2 is changed can produce a pattern of surface temperature change with zero global mean but non-zero change in net radiation at the top of the atmosphere (~ -0.5 Wm-2 in HadCM3).