Computer simulations of structures, energetics and dynamics of myoglobin center dot center dot center dot ligand complexes

Myoglobin has been studied in considerable detail using different experimental and computational techniques over the past decades. Recent developments in time-resolved spectroscopy have provided experimental data amenable to detailed atomistic simulations. The main theme of the present review are results on the structures, energetics and dynamics of ligands ( CO, NO) interacting with myoglobin from computer simulations. Modern computational methods including free energy simulations, mixed quantum mechanics/molecular mechanics simulations, and reactive molecular dynamics simulations provide insight into the dynamics of ligand dynamics in confined spaces complementary to experiment. Application of these methods to calculate and understand experimental observations for myoglobin interacting with CO and NO are presented and discussed.

Time-dependent orientation coupling in equilibrium polymer melts

The motion in concentrated polymer systems is described by either the Rouse or the reptation model, which both assume that the relaxation of each polymer chain is independent of the surrounding chains. This, however, is in contradiction with several experiments. In this Letter, we propose a universal description of orientation coupling in polymer melts in terms of the time-dependent coupling parameter κ(t). We use molecular dynamics simulations to show that the coupling parameter increases with time, reaching about 50% at long times, independently of the chain length or blend composition. This leads to predictions of component dynamics in mixtures of different molecular weights from the knowledge of monodisperse dynamics for unentangled melts. Finally, we demonstrate that entanglements do not play a significant role in the observed coupling. © 2010 The American Physical Society

The small open-economy New Keynesian Phillips Curve: empirical evidence and implied inflation dynamics

In this paper we apply GMM estimation to assess the relevance of domestic versus external determinants of CPI inflation dynamics in a sample of OECD countries typically classified as open economies. The analysis is based on a variant of the small open-economy New Keynesian Phillips Curve derived in Galí and Monacelli (Rev Econ Stud 72:707–734, 2005), where the novel feature is that expectations about fluctuations in the terms of trade enter explicitly. For most countries in our sample the expected relative change in the terms of trade emerges as the more relevant inflation driver than the contemporaneous domestic output gap.

Processes controlling DOC in pore water during simulated drought cycles in six different UK peats

The effect of episodic drought on dissolved organic carbon (DOC) dynamics in peatlands has been the subject of considerable debate, as decomposition and DOC production is thought to increase under aerobic conditions, yet decreased DOC concentrations have been observed during drought periods. Decreased DOC solubility due to drought-induced acidification driven by sulphur (S) redox reactions has been proposed as a causal mechanism; however evidence is based on a limited number of studies carried out at a few sites. To test this hypothesis on a range of different peats, we carried out controlled drought simulation experiments on peat cores collected from six sites across Great Britain. Our data show a concurrent increase in sulphate (SO4) and a decrease in DOC across all sites during simulated water table draw-down, although the magnitude of the relationship between SO4 and DOC differed between sites. Instead, we found a consistent relationship across all sites between DOC decrease and acidification measured by the pore water acid neutralising capacity (ANC). ANC provided a more consistent measure of drought-induced acidification than SO4 alone because it accounts for differences in base cation and acid anions concentrations between sites. Rewetting resulted in rapid DOC increases without a concurrent increase in soil respiration, suggesting DOC changes were primarily controlled by soil acidity not soil biota. These results highlight the need for an integrated analysis of hydrologically driven chemical and biological processes in peatlands to improve our understanding and ability to predict the interaction between atmospheric pollution and changing climatic conditions from plot to regional and global scales.

Modelling of the natural chlorine cycling in a coniferous stand: implications for chlorine-36 behaviour in a contaminated forest environment

Considered as one of the most available radionuclide in soileplant system, 36Cl is of potential concern for long-term management of radioactive wastes, due to its high mobility and its long half-life. To evaluate the risk of dispersion and accumulation of 36Cl in the biosphere as a consequence of a potential contamination, there is a need for an appropriate understanding of the chlorine cycling dynamics in the ecosystems. To date, a small number of studies have investigated the chlorine transfer in the ecosystem including the transformation of chloride to organic chlorine but, to our knowledge, none have modelled this cycle. In this study, a model involving inorganic as well as organic pools in soils has been developed and parameterised to describe the biogeochemical fate of chlorine in a pine forest. The model has been evaluated for stable chlorine by performing a range of sensitivity analyses and by comparing the simulated to the observed values. Finally a range of contamination scenarios, which differ in terms of external supply, exposure time and source, has been simulated to estimate the possible accumulation of 36Cl within the different compartments of the coniferous stand. The sensitivity study supports the relevancy of the model and its compartments, and has highlighted the chlorine transfers affecting the most the residence time of chlorine in the stand. Compared to observations, the model simulates realistic values for the chlorine content within the different forest compartments. For both atmospheric and underground contamination scenarios most of the chlorine can be found in its organic form in the soil. However, in case of an underground source, about two times less chlorine accumulates in the system and proportionally more chlorine leaves the system through drainage than through volatilisation.

Boundary-layer friction in midlatitude cyclone

Results from an idealized three-dimensional baroclinic life-cycle model are interpreted in a potential vorticity (PV) framework to identify the physical mechanisms by which frictional processes acting in the atmospheric boundary layer modify and reduce the baroclinic development of a midlatitude storm. Considering a life cycle where the only non-conservative process acting is boundary-layer friction, the rate of change of depth-averaged PV within the boundary layer is governed by frictional generation of PV and the flux of PV into the free troposphere. Frictional generation of PV has two contributions: Ekman generation, which is directly analogous to the well-known Ekman-pumping mechanism for barotropic vortices, and baroclinic generation, which depends on the turning of the wind in the boundary layer and low-level horizontal temperature gradients. It is usually assumed, at least implicitly, that an Ekman process of negative PV generation is the mechanism whereby friction reduces the strength and growth rates of baroclinic systems. Although there is evidence for this mechanism, it is shown that baroclinic generation of PV dominates, producing positive PV anomalies downstream of the low centre, close to developing warm and cold fronts. These PV anomalies are advected by the large-scale warm conveyor belt flow upwards and polewards, fluxed into the troposphere near the warm front, and then advected westwards relative to the system. The result is a thin band of positive PV in the lower troposphere above the surface low centre. This PV is shown to be associated with a positive static stability anomaly, which Rossby edge wave theory suggests reduces the strength of the coupling between the upper- and lower-level PV anomalies, thereby reducing the rate of baroclinic development. This mechanism, which is a result of the baroclinic dynamics in the frontal regions, is in marked contrast with simple barotropic spin-down ideas. Finally we note the implications of these frictionally generated PV anomalies for cyclone forecasting.

Regulation of surface water quality in a Cretaceous chalk catchment, UK: an assessment of the relative importance of instream and wetland processes

To investigate the relative importance of instream nutrient spiralling and wetland transformation processes on surface water quality, total nitrogen (TN) and total phosphorus (TP) concentrations in a 200 m reach of the River Lambourn in the south-east of England were monitored over a 2-year period. In addition, the soil pore water nutrient dynamics in a riparian ecosystem adjacent to the river were investigated. Analysis of variance indicated that TN, TP and suspended sediment concentrations recorded upstream of the wetland were statistically significantly higher (P<0.05) than those downstream of the site. Such results suggest that the wetland was performing a nutrient retention function. Indeed, analysis of soil pore waters within the site show that up to 85% of TN and 70% of TP was removed from water flowing through the wetland during baseflow conditions, thus supporting the theory that the wetland played an important role in the regulation of surface water quality at the site. However, the small variations observed (0.034 mg TN l-1 and 0.031 mg P l-1) are consistent with the theory of nutrient spiralling suggesting that both instream and wetland retention processes have a causal effect on surface water quality.

A change detection approach to flood mapping in urban areas using TerraSAR-X

Very high-resolution Synthetic Aperture Radar sensors represent an alternative to aerial photography for delineating floods in built-up environments where flood risk is highest. However, even with currently available SAR image resolutions of 3 m and higher, signal returns from man-made structures hamper the accurate mapping of flooded areas. Enhanced image processing algorithms and a better exploitation of image archives are required to facilitate the use of microwave remote sensing data for monitoring flood dynamics in urban areas. In this study a hybrid methodology combining radiometric thresholding, region growing and change detection is introduced as an approach enabling the automated, objective and reliable flood extent extraction from very high-resolution urban SAR images. The method is based on the calibration of a statistical distribution of “open water” backscatter values inferred from SAR images of floods. SAR images acquired during dry conditions enable the identification of areas i) that are not “visible” to the sensor (i.e. regions affected by ‘layover’ and ‘shadow’) and ii) that systematically behave as specular reflectors (e.g. smooth tarmac, permanent water bodies). Change detection with respect to a pre- or post flood reference image thereby reduces over-detection of inundated areas. A case study of the July 2007 Severn River flood (UK) observed by the very high-resolution SAR sensor on board TerraSAR-X as well as airborne photography highlights advantages and limitations of the proposed method. We conclude that even though the fully automated SAR-based flood mapping technique overcomes some limitations of previous methods, further technological and methodological improvements are necessary for SAR-based flood detection in urban areas to match the flood mapping capability of high quality aerial photography.

Fair trade and European public procurement: legal principles and governance dynamics

Purpose The article examines principles of Fair Trade in public procurement in Europe, focusing on legal dimensions related to the European Public Procurement Directives. Design/methodology/approach The article situates public procurement of Fair Trade products in relation to the rise of non-state regulatory initiatives, highlighting how they have entered into new governance dynamics in the public sector and play a part in changing practices in sustainable procurement. A review of legal position on Fair Trade in procurement law is informed by academic research and campaigning experience from the Fair Trade Advocacy Office. Findings Key findings are that the introduction of Fair Trade products into European public procurement has been marked by legal ambiguity, having developed outside comprehensive policy or legal guidelines. Following a 2012 ruling by the Court of Justice of the European Union, it is suggested that the legal position for Fair Trade in procurement has become clearer, and that forthcoming change to the Public Procurement Directives may facilitate the uptake of fair trade products by public authorities. However potential for future expansion of the public sector ‘market’ for Fair Trade is approached with caution: purchasing Fair Trade products as a marker of sustainability, which started to be embedded within procurement practice in the 2000s, is challenged by current European public austerity measures. Research limitations/implications Suggestions for future research include the need for systematic cross-institutional and multi-country comparison of the legal and governance dimensions of procurement practice with regard to Fair Trade. Practical implications A clarification of current state-of-play with regard to legal aspects of fair trade in public procurement of utility for policy and advocacy discussion. Originality/value The article provides needed elaboration on an under researched topic area of value to academia and policy makers.