Supramolecular assemblies of metal ions in complex bimetallic and trimetallic salts based on hexacyanoferrate(III) ion

Two complex heterometallic salts with formulae Tl-6[Fe(CN)(6)](1) (33)(NO3)(OH) (1) and [Co(bpy)(2)(CN)(2)](2){[Ag(CN)(2)](0) (5)[Fe(CN)(6)](0) (5)} 8H(2)O (2) have been synthesized and fully characterized Single crystal X-ray analyses reveal that compound 1 is comprised of discrete Tl+ cations and [Fe(CN)(6)](3-) anions together with OH- and NO3- anions Compound 2 contains [Co(bpy)(2)(CN)(2)](+) cations and {[Ag(CN)(2)][Fe(CN)(6)]}(-) anions together with eight molecules of water of crystallization Both structures form unprecedented three-dimensional supramolecular networks via non covalent interactions Another important observation is that the stereochemically active inert (lone) pair present on Tl+ plays little role in controlling the structure of 1 The water molecules in 2 play important roles in providing stability organizing a supramolecular network through hydrogen bonding In the syntheses of 1 and 2 Fe(II) is oxidized to Fe(III) and Co(II) to Co(III) respectively facilitating the formation of the salts that are obtained Both compounds exhibit photoluminescence emission in solution near the visible region.

A value chain approach to animal diseases risk management: technical foundations and practical framework for field application

Classical risk assessment approaches for animal diseases are influenced by the probability of release, exposure and consequences of a hazard affecting a livestock population. Once a pathogen enters into domestic livestock, potential risks of exposure and infection both to animals and people extend through a chain of economic activities related to producing, buying and selling of animals and products. Therefore, in order to understand economic drivers of animal diseases in different ecosystems and to come up with effective and efficient measures to manage disease risks from a country or region, the entire value chain and related markets for animal and product needs to be analysed to come out with practical and cost effective risk management options agreed by actors and players on those value chains. Value chain analysis enriches disease risk assessment providing a framework for interdisciplinary collaboration, which seems to be in increasing demand for problems concerning infectious livestock diseases. The best way to achieve this is to ensure that veterinary epidemiologists and social scientists work together throughout the process at all levels.

The accuracy of valuations: expectation and reality

The relationship between valuations and the subsequent sale price continues to be a matter of both theoretical and practical interest. This paper reports the analysis of over 700 property sales made during the 1974/90 period. Initial results imply an average under-valuation of 7% and a standard error of 18% across the sample. A number of techniques are applied to the data set using other variables such as the region, the type of property and the return from the market to explain the difference between the valuation and the subsequent sale price. The analysis reduces the unexplained error; the bias is fully accounted for and the standard error is reduced to 15.3%. This model finds that about 6% of valuations over-estimated the sale price by more than 20% and about 9% of the valuations under-estimated the sale prices by more than 20%. The results suggest that valuations are marginally more accurate than might be expected, both from consideration of theoretical considerations and from comparison with the equivalent valuation in equity markets.

Analysis of 16S rDNA sequences from pathogenic Leptospira serovars and use of single nucleotide polymorphisms for rapid speciation by D-HPLC

Leptospira have a worldwide distribution and include important zoonotic pathogens yet diagnosis and differentiation still tend to rely on traditional bacteriological and serological approaches. In this study a 1.3 kb fragment of the rrs gene (16S rDNA) was sequenced from a panel of 22 control strains, representing serovars within the pathogenic species Leptospira interrogans, Leptospira borgpetersenii, and Leptospira kirschneri, to identify single nucleotide polymorphisms (SNPs). These were identified in the 5' variable region of the 16S sequence and a 181 bp PCR fragment encompassing this region was used for speciation by Denaturing High Performance Liquid Chromatography (D-HPLC). This method was applied to eleven additional species, representing pathogenic, non-pathogenic and intermediate species and was demonstrated to rapidly differentiate all but 2 of the non-pathogenic Leptospira species. The method was applied successfully to infected tissues from field samples proving its value for diagnosing leptospiral infections found in animals in the UK. Crown Copyright (C) 2010 Published by Elsevier Ltd. All rights reserved.

A global view of the extratropical tropopause transition layer from Atmospheric Chemistry Experiment Fourier Transform Spectrometer O3, H2O, and CO

The global behavior of the extratropical tropopause transition layer (ExTL) is investigated using O3, H2O, and CO measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on Canada’s SCISAT-1 satellite obtained between February 2004 and May 2007. The ExTL depth is derived using H2O-O3 and CO-O3 correlations. The ExTL top derived from H2O-O3 shows an increase from roughly 1–1.5 km above the thermal tropopause in the subtropics to 3–4 km (2.5–3.5 km) in the north (south) polar region, implying somewhat weaker tropospherestratosphere- transport in the Southern Hemisphere. The ExTL bottom extends ~1 km below the thermal tropopause, indicating a persistent stratospheric influence on the troposphere at all latitudes. The ExTL top derived from the CO-O3 correlation is lower, at 2 km or ~345 K (1.5 km or ~335 K) in the Northern (Southern) Hemisphere. Its annual mean coincides with the relative temperature maximum just above the thermal tropopause. The vertical CO gradient maximizes at the thermal tropopause, indicating a local minimum in mixing within the tropopause region. The seasonal changes in and the scales of the vertical H2O gradients show a similar pattern as the static stability structure of the tropopause inversion layer (TIL), which provides observational support for the hypothesis that H2O plays a radiative role in forcing and maintaining the structure of the TIL.

Using the significant dust deposition event on the glaciers of Mt. Elbrus, Caucasus Mountains, Russia on 5 May 2009 to develop a method for dating and provenancing of desert dust events recorded in snow pack.

A significant desert dust deposition event occurred on Mt. Elbrus, Caucasus Mountains, Russia on 5 May 2009, where the deposited dust later appeared as a brown layer in the snow pack. An examination of dust transportation history and analysis of chemical and physical properties of the deposited dust were used to develop a new approach for high-resolution provenancing of dust deposition events recorded in snow pack using multiple independent techniques. A combination of SEVIRI red-green-blue composite imagery, MODIS atmospheric optical depth fields derived using the Deep Blue algorithm, air mass trajectories derived with HYSPLIT model and analysis of meteorological data enabled identification of dust source regions with high temporal (hours) and spatial (ca. 100 km) resolution. Dust, deposited on 5 May 2009, originated in the foothills of the Djebel Akhdar in eastern Libya where dust sources were activated by the intrusion of cold air from the Mediterranean Sea and Saharan low pressure system and transported to the Caucasus along the eastern Mediterranean coast, Syria and Turkey. Particles with an average diameter below 8 μm accounted for 90% of the measured particles in the sample with a mean of 3.58 μm, median 2.48 μm and the dominant mode of 0.60 μm. The chemical signature of this long-travelled dust was significantly different from the locally-produced dust and close to that of soils collected in a palaeolake in the source region, in concentrations of hematite and oxides of aluminium, manganese, and magnesium. Potential addition of dust from a secondary source in northern Mesopotamia introduced uncertainty in the provenancing of dust from this event. Nevertheless, the approach adopted here enables other dust horizons in the snowpack to be linked to specific dust transport events recorded in remote sensing and meteorological data archives.

The extratropical upper troposphere and lower stratosphere

The extratropical upper troposphere and lower stratosphere (Ex-UTLS) is a transition region between the stratosphere and the troposphere. The Ex-UTLS includes the tropopause, a strong static stability gradient and dynamic barrier to transport. The barrier is reflected in tracer profiles. This region exhibits complex dynamical, radiative, and chemical characteristics that place stringent spatial and temporal requirements on observing and modeling systems. The Ex-UTLS couples the stratosphere to the troposphere through chemical constituent transport (of, e.g., ozone), by dynamically linking the stratospheric circulation with tropospheric wave patterns, and via radiative processes tied to optically thick clouds and clear-sky gradients of radiatively active gases. A comprehensive picture of the Ex-UTLS is presented that brings together different definitions of the tropopause, focusing on observed dynamical and chemical structure and their coupling. This integral view recognizes that thermal gradients and dynamic barriers are necessarily linked, that these barriers inhibit mixing and give rise to specific trace gas distributions, and that there are radiative feedbacks that help maintain this structure. The impacts of 21st century anthropogenic changes to the atmosphere due to ozone recovery and climate change will be felt in the Ex-UTLS, and recent simulations of these effects are summarized and placed in context.

The 20 February 2010 Madeira flash-floods: synoptic analysis and extreme rainfall assessment

This study aims to characterise the rainfall exceptionality and the meteorological context of the 20 February 2010 flash-floods in Madeira (Portugal). Daily and hourly precipitation records from the available rain-gauge station networks are evaluated in order to reconstitute the temporal evolution of the rainstorm, as its geographic incidence, contributing to understand the flash-flood dynamics and the type and spatial distribution of the associated impacts. The exceptionality of the rainstorm is further confirmed by the return period associated with the daily precipitation registered at the two long-term record stations, with 146.9 mm observed in the city of Funchal and 333.8 mm on the mountain top, corresponding to an estimated return period of approximately 290 yr and 90 yr, respectively. Furthermore, the synoptic associated situation responsible for the flash-floods is analysed using different sources of information, e.g., weather charts, reanalysis data, Meteosat images and radiosounding data, with the focus on two main issues: (1) the dynamical conditions that promoted such anomalous humidity availability over the Madeira region on 20 February 2010 and (2) the uplift mechanism that induced deep convection activity.

Analysis of incoherent scatter radar data from non-thermal F-region plasma

A procedure is presented for fitting incoherent scatter radar data from non-thermal F-region ionospheric plasma, using theoretical spectra previously predicted. It is found that values of the shape distortion factor D∗, associated with deviations of the ion velocity distribution from a Maxwellian distribution, and ion temperatures can be deduced (the results being independent of the path of iteration) if the angle between the line-of-sight and the geomagnetic field is larger than about 15–20°. The procedure can be used with one or both of two sets of assumptions. These concern the validity of the adopted model for the line-of-sight ion velocity distribution in the one case or for the full three-dimensional ion velocity distribution function in the other. The distribution function employed was developed to describe the line-of-sight velocity distribution for large aspect angles, but both experimental data and Monte Carlo simulations indicate that the form of the field-perpendicular distribution can also describe the distribution at more general aspect angles. The assumption of this form for the line-of-sight velocity distribution at a general aspect angle enables rigorous derivation of values of the one-dimensional, line-of-sight ion temperature. With some additional assumptions (principally that the field-parallel distribution is always Maxwellian and there is a simple relationship between the ion temperature anisotropy and the distortion of the field-perpendicular distribution from a Maxwellian), fits to data for large aspect angles enable determination of line-of-sight temperatures at all aspect angles and hence, of the average ion temperature and the ion temperature anisotropy. For small aspect angles, the analysis is restricted to the determination of the line-of-sight ion temperature because the theoretical spectrum is insensitive to non-thermal effects when the plasma is viewed along directions almost parallel to the magnetic field. This limitation is expected to apply to any realistic model of the ion velocity distribution function and its consequences are discussed. Fit strategies which allow for mixed ion composition are also considered. Examples of fits to data from various EISCAT observing programmes are presented.

Oblique h.f. radiowave propagation in the main trough region of the ionosphere

The propagation of 7.335 MHz, c.w. signals over a 5212 km sub-auroral, west-east path is studied. Measurements and semi-empirical predictions are made of the amplitude distributions and Doppler shifts of the received signals. The observed amplitude distribution is fitted with one produced by a numerical fading model, yielding the power losses suffered by the signals during propagation via the predominating modes. The signals are found to suffer exceptionally low losses at certain local times under geomagnetically quiet conditions. The mid-latitude trough in the F2 peak ionization density is predicted by a statistical model to be at the latitudes of this path at these times and at low Kp values. A sharp cut-off in low-power losses at a mean Kp of 2.75 strongly implicates the trough in the propagation of these signals. The Doppler shifts observed at these times cannot be explained by a simple ray-tracing model. It is shown however, that a simple extension of this model to allow for the trough can reproduce the form of the observed diurnal variation.

Pre-Columbian land use in the ring-ditch region of the Bolivian Amazon

The nature and extent of pre-Columbian (pre-1492 AD) human impact in Amazonia is a contentious issue. The Bolivian Amazon has yielded some of the most impressive evidence for large and complex pre-Columbian societies in the Amazon basin, yet there remains relatively little data concerning the land use of these societies over time. Palaeoecology, when integrated with archaeological data, has the potential to fill these gaps in our knowledge. We present a 6,000-year record of anthropogenic burning, agriculture and vegetation change, from an oxbow lake located adjacent to a pre-Columbian ring-ditch in north-east Bolivia (13°15’44” S, 63°42’37” W). Human occupation around the lake site is inferred from pollen and phytoliths of maize (Zea mays L.) and macroscopic charcoal evidence of anthropogenic burning. First occupation around the lake was radiocarbon dated to ~2500 years BP. The persistence of maize in the record from ~1850 BP suggests that it was an important crop grown in the ringditch region in pre-Columbian times, and abundant macroscopic charcoal suggests that pre-Columbian land management entailed more extensive burning of the landscape than the slash-and-burn agriculture practised around the site today. The site was occupied continuously until near-modern times, although there is evidence for a decline in agricultural intensity or change in land use strategy, and possible population decline, from ~600-500 BP. The long and continuous occupation, which predates the establishment of rainforest in the region, suggests that pre-Columbian land use may have had a significant influence on ecosystem development at this site over the last ~2000 years.

Genetic diversity at the Dhn3 locus in Turkish Hordeum spontaneum populations with comparative structural analyses

We analysed Hordeum spontaneum accessions from 21 different locations to understand the genetic diversity of HsDhn3 alleles and effects of single base mutations on the intrinsically disordered structure of the resulting polypeptide (HsDHN3). HsDHN3 was found to be YSK2-type with a low-frequency 6-aa deletion in the beginning of Exon 1. There is relatively high diversity in the intron region of HsDhn3 compared to the two exon regions. We have found subtle differences in K segments led to changes in amino acids chemical properties. Predictions for protein interaction profiles suggest the presence of a protein-binding site in HsDHN3 that coincides with the K1 segment. Comparison of DHN3 to closely related cereals showed that all of them contain a nuclear localization signal sequence flanking to the K1 segment and a novel conserved region located between the S and K1 segments [E(D/T)DGMGGR]. We found that H. vulgare, H. spontaneum, and Triticum urartu DHN3s have a greater number of phosphorylation sites for protein kinase C than other cereal species, which may be related to stress adaptation. Our results show that the nature and extent of mutations in the conserved segments of K1 and K2 are likely to be key factors in protection of cells.

Pre-Columbian ring ditch construction and land use on a “chocolate forest island” in the Bolivian Amazon

We present a palaeoecological investigation of pre-Columbian land use in the savannah “forest island” landscape of north-east Bolivian Amazonia. A 5700 year sediment core from La Luna Lake, located adjacent to the La Luna forest island site, was analysed for fossil pollen and charcoal. We aimed to determine the palaeoenvironmental context of pre-Columbian occupation on the site and assess the environmental impact of land use in the forest island region. Evidence for anthropogenic burning and Zea mays L. cultivation began ~2000 cal a BP, at a time when the island was covered by savannah, under drier-than-present climatic conditions. After ~1240 cal a BP burning declined and afforestation occurred. We show that construction of the ring ditch, which encircles the island, did not involve substantial deforestation. Previous estimates of pre-Columbian population size in this region, based upon labour required for forest clearance, should therefore be reconsidered. Despite the high density of economically useful plants, such as Theobroma cacao, in the modern forest, no direct pollen evidence for agroforestry was found. However, human occupation is shown to pre-date and span forest expansion on this site, suggesting that here, and in the wider forest island region, there is no truly pre-anthropogenic ‘pristine’ forest.

A review of drought in the Middle East and Southwest Asia

The Middle East and Southwest Asia comprise a region that is water-stressed, societally vulnerable, and prone to severe droughts. Large-scale climate variability, particularly La Niña, appears to play an important role in region-wide drought, including the two most severe of the last fifty years—1999-2001 and 2007-2008—with implications for drought forecasting. Important dynamical factors include orography, thermodynamic influence on vertical motion, storm track changes, and moisture transport. Vegetation in the region is strongly impacted by drought and may provide an important feedback mechanism. In future projections, drying of the eastern Mediterranean is a robust feature, as are temperature increases throughout the region, which will affect evaporation and the timing and intensity of snowmelt. Vegetation feedbacks may become more important in a warming climate. There are a wide range of outstanding issues for understanding, monitoring, and predicting drought in the region, including: dynamics of the regional storm track, the relative importance of the range of dynamical mechanisms related to drought, regional coherence of drought, the relationship between synoptic-scale mechanisms and drought, predictability of vegetation and crop yields, stability of remote influences, data uncertainty, and the role of temperature. Development of a regional framework for cooperative work and dissemination of information and existing forecasts would speed understanding and make better use of available information.