The role of space charge formation in the generation of thermally stimulated current (TSC) spectroscopy data for a model amorphous drug system

Thermally stimulated current (TSC) spectroscopy is attracting increasing attention as a means of materials characterization, particularly in terms of measuring slow relaxation processes in solid samples. However, wider use of the technique within the pharmaceutical field has been inhibited by difficulties associated with the interpretation of TSC data, particularly in terms of deconvoluting dipolar relaxation processes from charge distribution phenomena. Here, we present evidence that space charge and electrode contact effects may play a significant role in the generation of peaks that have thus far proved difficult to interpret. We also introduce the use of a stabilization temperature in order to control the space charge magnitude. We have studied amorphous indometacin as a model drug compound and have varied the measurement parameters (stabilization and polarization temperatures), interpreting the changes in spectral composition in terms of charge redistribution processes. More specifically, we suggested that charge drift and diffusion processes, charge injection from the electrodes and high activation energy charge redistribution processes may all contribute to the appearance of shoulders and 'spurious' peaks. We present recommendations for eliminating or reducing these effects that may allow more confident interpretation of TSC data.

Simulation of mackerel (Scomber scombrus) recruitment with an individual-based model and comparison with field data

An individual-based model (IBM) for the simulation of year-to-year survival during the early life-history stages of the north-east Atlantic stock of mackerel (Scomber scombrus) was developed within the EU funded Shelf-Edge Advection, Mortality and Recruitment (SEAMAR) programme. The IBM included transport, growth and survival and was used to track the passive movement of mackerel eggs, larvae and post-larvae and determine their distribution and abundance after approximately 2 months of drift. One of the main outputs from the IBM, namely distributions and numbers of surviving post-larvae, are compared with field data as recruit (age-0/age-1 juveniles) distribution and abundance for the years 1998, 1999 and 2000. The juvenile distributions show more inter-annual and spatial variability than the modelled distributions of survivors; this may be due to the restriction of using the same initial egg distribution for all 3 yr of simulation. The IBM simulations indicate two main recruitment areas for the north-east Atlantic stock of mackerel, these being Porcupine Bank and the south-eastern Bay of Biscay. These areas correspond to areas of high juvenile catches, although the juveniles generally have a more widespread distribution than the model simulations. The best agreement between modelled data and field data for distribution (juveniles and model survivors) is for the year 1998. The juvenile catches in different representative nursery areas are totalled to give a field abundance index (FAI). This index is compared with a model survivor index (MSI) which is calculated from the total of survivors for the whole spawning season. The MSI compares favourably with the FAI for 1998 and 1999 but not for 2000; in this year, juvenile catches dropped sharply compared with the previous years but there was no equivalent drop in modelled survivors.

A Note On Tidal Asymmetry In The Severn Estuary

A one-dimensional, non-linear numerical model is used to investigate the tidally averaged frictional stress and set-up of water level due to tidal asymmetry in the Severn Estuary; these quantities depend on the overtides in the region. A linearized model of the overtides is applied to calculations of the M4 currents in order to delineate the mechanisms responsible for their generation. The relative importance of individual non-linear mechanisms to the tidally averaged stress and set-up is determined; these mechanisms are interactions between tidal flow and changes in depth or breadth over a cross-section, frictional interaction between the tidal flow and Stokes drift, interaction between the tidal fluctuations in water depth and frictional retardation and non-linear advection.

Latitudinal phytoplankton distribution and the neutral theory of biodiversity

Aim Recent studies have suggested that global diatom distributions are not limited by dispersal, in the case of both extant species and fossil species, but rather that environmental filtering explains their spatial patterns. Hubbell's neutral theory of biodiversity provides a framework in which to test these alternatives. Our aim is to test whether the structure of marine phytoplankton (diatoms, dinoflagellates and coccolithophores) assemblages across the Atlantic agrees with neutral theory predictions. We asked: (1) whether intersite variance in phytoplankton diversity is explained predominantly by dispersal limitation or by environmental conditions; and (2) whether species abundance distributions are consistent with those expected by the neutral model. Location Meridional transect of the Atlantic (50 degrees N50 degrees S). Methods We estimated the relative contributions of environmental factors and geographic distance to phytoplankton composition using similarity matrices, Mantel tests and variation partitioning of the species composition based upon canonical ordination methods. We compared the species abundance distribution of phytoplankton with the neutral model using Etienne's maximum-likelihood inference method. Results Phytoplankton communities are slightly more determined by niche segregation (24%), than by dispersal limitation and ecological drift (17%). In 60% of communities, the assumption of neutrality in species' abundance distributions could not be rejected. In tropical zones, where oceanic gyres enclose large stable water masses, most communities showed low species immigration rates; in contrast, we infer that communities in temperate areas, out of oligotrophic gyres, have higher rates of species immigration. Conclusions Phytoplankton community structure is consistent with partial niche assembly and partial dispersal and drift assembly (neutral processes). The role of dispersal limitation is almost as important as habitat filtering, a fact that has been largely overlooked in previous studies. Furthermore, the polewards increase in immigration rates of species that we have discovered is probably caused by water mixing conditions and productivity.

Genotyping an Emiliania huxleyi (Prymnesiophyceae) bloom event in the North Sea reveals evidence of asexual reproduction

Due to the unprecedented rate at which our climate is changing, the ultimate consequence for many species is likely to be either extinction or migration to an alternate habitat. Certain species might, however, evolve at a rate that could make them resilient to the effects of a rapidly changing environment. This scenario is most likely to apply to species that have large population sizes and rapid generation times, such that the genetic variation required for adaptive evolution can be readily supplied. Emiliania huxleyi (Lohm.) Hay and Mohler (Prymnesiophyceae) is likely to be such a species as it is the most conspicuous extant calcareous phytoplankton species in our oceans with generation times of 1 day−1. Here we report on a validated set of microsatellites, in conjunction with the coccolithophore morphology motif genetic marker, to genotype 93 clonal isolates collected from across the world. Of these, 52 came from a single bloom event in the North Sea collected on the D366 UK Ocean Acidification cruise in June-July 2011. There were 26 multilocus genotypes (MLGs) encountered only once in the North Sea bloom and 8 MLGs encountered twice or up to six times. Each of these repeated MLGs exhibited Psex values of less than 0.05 indicating each repeated MLG was the product of asexual reproduction and not separate meiotic events. In addition, we show that the two most polymorphic microsatellite loci, EHMS37 and P01E05, are reporting on regions likely undergoing rapid genetic drift during asexual reproduction. Despite the small sample size, there were many more repeated genotypes than previously reported for other bloom-forming phytoplankton species, including a previously genotyped E. huxleyi bloom event. This study challenges our current assumption that sex is the predominant mode of reproduction during bloom events. Whilst genetic diversity is high amongst extant populations of E. huxleyi, the root cause for this diversity and ultimate fate of these populations still requires further examination. Nonetheless, we show that certain CMM genotypes are found everywhere; while others appear to have a regional bias.

Implications of streamlining theory for microbial ecology

Whether a small cell, a small genome or a minimal set of chemical reactions with self-replicating properties, simplicity is beguiling. As Leonardo da Vinci reportedly said, 'simplicity is the ultimate sophistication'. Two diverging views of simplicity have emerged in accounts of symbiotic and commensal bacteria and cosmopolitan free-living bacteria with small genomes. The small genomes of obligate insect endosymbionts have been attributed to genetic drift caused by small effective population sizes (Ne). In contrast, streamlining theory attributes small cells and genomes to selection for efficient use of nutrients in populations where Ne is large and nutrients limit growth. Regardless of the cause of genome reduction, lost coding potential eventually dictates loss of function. Consequences of reductive evolution in streamlined organisms include atypical patterns of prototrophy and the absence of common regulatory systems, which have been linked to difficulty in culturing these cells. Recent evidence from metagenomics suggests that streamlining is commonplace, may broadly explain the phenomenon of the uncultured microbial majority, and might also explain the highly interdependent (connected) behavior of many microbial ecosystems. Streamlining theory is belied by the observation that many successful bacteria are large cells with complex genomes. To fully appreciate streamlining, we must look to the life histories and adaptive strategies of cells, which impose minimum requirements for complexity that vary with niche.

Variation in elemental stoichiometry of the marine diatomThalassiosira weissflogii(Bacillariophyceae) in response to combined nutrient stress and changes in carbonate chemistry

The combined consequences of the multi-stressors of pH and nutrient availability upon the growth of a marine diatom were investigated. Thalassiosira weissflogii was grown in N- or P-limited batch culture in sealed systems, with pH commencing at 8.2 (extant conditions) or 7.6 (ocean acidification [OA] conditions), and then pH was allowed to either drift with growth, or was held fixed. Results indicated that within the pH range tested, the stability of environmental pH rather than its value (i.e., OA vs. extant) fundamentally influenced biomass accumul-ation and C:N:P stoichiometry. Despite large changes in total alkalinity in the fixed pH systems, final biomass production was consistently greater in these systems than that in drifting pH systems. In drift systems, pH increased to exceed pH 9.5, a level of alkalinity that was inhibitory to growth. No statis-tically significant differences between pH treatments were measured for N:C, P:C or N:P ratios during nutrient-replete growth, although the diatom expre-ssed greater plasticity in P:C and N:P ratios than in N:C during this growth phase. During nutrient-deplete conditions, the capacity for uncoupled carbon fixa-tion at fixed pH was considerably greater than that measured in drift pH systems, leading to strong contrasts in C:N:P stoichiometry between these treatments. Whether environmental pH was stable or drifted directly influenced the extent of physiological stress. In contrast, few distinctions could be drawn between extant versus OA conditions for cell physiology.

Estimating Oceanic Primary Production Using Vertical Irradiance and Chlorophyll Profiles from Ocean Gliders in the North Atlantic

An autonomous underwater vehicle (Seaglider) has been used to estimate marine primary production (PP) using a combination of irradiance and fluorescence vertical profiles. This method provides estimates for depth-resolved and temporally evolving PP on fine spatial scales in the absence of ship-based calibrations. We describe techniques to correct for known issues associated with long autonomous deployments such as sensor calibration drift and fluorescence quenching. Comparisons were made between the Seaglider, stable isotope (13C), and satellite estimates of PP. The Seaglider-based PP estimates were comparable to both satellite estimates and stable isotope measurements.

Effect of habitat fragmentation on levels and patterns of genetic diversity in natural populations of the peat moss Polytrichum commune

Peat bogs represent unique ecosystems that are under particular threat from fragmentation due to peat harvesting, with only 38% of the original peatland in Europe remaining intact and unaffected by peat cutting, drainage and silviculture. In this study, we have used microsatellite markers to determine levels and patterns of genetic diversity in both cut and uncut natural populations of the peat moss Polytrichum commune. Overall diversity levels suggest that there is more genetic variation present than had previously been assumed for bryophytes. Despite this, diversity values from completely cut bogs were found to be lower than those from uncut peatlands (average 0.729 versus 0.880). In addition, the genetic diversity was more highly structured in the cut populations, further suggesting that genetic drift is already affecting genetic diversity in peat bogs subjected to fragmentation.

Differential lifetime success and performance of native and non-native Atlantic salmon examined under communal natural conditions.

The lifetime success and performance characteristics of communally reared offspring of wild native Burrishoole (native), ranched native (ranched) and non-native (non-native) Atlantic salmon Salmo salar from the adjacent Owenmore River were compared. Non-native year parr showed a substantial downstream migration, which was not shown by native and ranched parr. This appears to have been an active migration rather than competitive displacement and may reflect an adaptation to environmental or physiographic conditions within the Owenmore River catchment where the main nursery habitat is downstream of the spawning area. There were no differences between native and ranched in smolt output or adult return. Both of these measures, however, were significantly lower for the non-native group. A greater proportion of the non-native Atlantic salmon was taken in the coastal drift nets compared to the return to the Burrishoole system, probably as a result of the greater size of the non-native fish. The overall lifetime success of the non-native group, from fertilized egg to returning adult, was some 35% of native and ranched. The ranched group showed a significantly greater male parr maturity, a greater proportion of 1+ year smolts, and differences in sex ratio and timing of freshwater entry of returning adults compared to native, which may have fitness implications under specific conditions.

Fault Diagnosis in Internal Combustion Engines Using Nonlinear Multivariate Statistics

This paper presents a statistical-based fault diagnosis scheme for application to internal combustion engines. The scheme relies on an identified model that describes the relationships between a set of recorded engine variables using principal component analysis (PCA). Since combustion cycles are complex in nature and produce nonlinear relationships between the recorded engine variables, the paper proposes the use of nonlinear PCA (NLPCA). The paper further justifies the use of NLPCA by comparing the model accuracy of the NLPCA model with that of a linear PCA model. A new nonlinear variable reconstruction algorithm and bivariate scatter plots are proposed for fault isolation, following the application of NLPCA. The proposed technique allows the diagnosis of different fault types under steady-state operating conditions. More precisely, nonlinear variable reconstruction can remove the fault signature from the recorded engine data, which allows the identification and isolation of the root cause of abnormal engine behaviour. The paper shows that this can lead to (i) an enhanced identification of potential root causes of abnormal events and (ii) the masking of faulty sensor readings. The effectiveness of the enhanced NLPCA based monitoring scheme is illustrated by its application to a sensor fault and a process fault. The sensor fault relates to a drift in the fuel flow reading, whilst the process fault relates to a partial blockage of the intercooler. These faults are introduced to a Volkswagen TDI 1.9 Litre diesel engine mounted on an experimental engine test bench facility.

Care proceedings: Exploring the relationship between case duration and achieving permanency for the child

The 1989 Children Act in England and Wales and the derivative 1995 Children (NI) Order in Northern Ireland provide the legislative framework within which issues pertaining to the care and supervision of children that come before the Courts are examined. Both pieces of legislation were intended to address a number of problems with the way that such issues were dealt with by the Court, particularly the tendency for proceedings to become protracted and for children to ‘drift’ in care as a consequence. The imposition of the ‘No Delay’ principle in both jurisdictions was designed specifically to address these concerns. However, since the introduction of both the 1989 Children Act (implemented in October 1991) and the 1995 Children (NI) Order (implemented in November 1996), there has been a steady increase in the average duration of proceedings and concerns remain about the impact that this may be having upon the children involved. This paper presents the findings of a research study (McSherry et al., 2004) that explored the complex relationship between the duration of care proceedings and costs to children in terms of the likelihood of achieving permanency.

Counterbalancing forces in electromigration

In electromigration (EM) experiments on metallic wires, a flux of atoms can lead to motion of the centre of mass (COM) of the wire. Hence, it may be tempting to assume that the flow of current produces a net force on the wire as a whole. We point out, on the basis of known momentum-balance arguments, that the net force on a metallic wire due to a passing steady-state current is zero. This is possible, because in addition to EM driving forces, acting on scattering centres, there are counterbalancing forces, acting on the rest of the system. Drift of the COM in EM experiments occurs inevitably because the substrate keeps the crystal lattice of the wire fixed, while allowing diffusion of defects in the bulk of the wire. This drift is not evidence for a net force on the wire.

Spectroscopic measurements of phase-resolved electron energy distribution functions in RF-excited discharges

The reliable measurement of the electron energy distribution function (EEDF) of plasmas is one of the most important subjects of plasma diagnostics, because this piece of information is the key to understand basic discharge mechanisms. Specific problems arise in the case of RF-excited plasmas, since the properties of electrons are subject to changes on a nanosecond time scale and show pronounced spatial anisotropy. We report on a novel spectroscopic method for phase- and space-resolved measurements of the electron energy distribution function of energetic (> 12 eV) electrons in RF discharges. These electrons dominate excitation and ionization processes and are therefore of particular interest. The technique is based on time-dependent measurements during the RF cycle of excited-state populations of rare gases admixed in small fractions. These measurements yield � in combination with an analytical model � detailed information on the excitation processes. Phase-resolved optical emission spectroscopy allows us to overcome the difficulties connected with the very low densities (107�109 cm�3) and the transient character of the electrons in the sheath region. The EEDF of electrons accelerated in the sheath region can be described by a shifted Maxwellian with a drift velocity component in direction of the electric field. The method yields the high-energy tail of the EEDF on an absolute scale. The applicability of the method is demonstrated at a capacitively coupled RF discharge in hydrogen.

Predation on mayfly nymph, Baetis rhodani, by native and introduced Gammarus: direct effects and the facilitation of predation by salmonids.

1. In a series of laboratory experiments, we assessed the predatory nature of the native Irish amphipod, Gammarus duebeni celticus, and the introduced G. pulex, towards the mayfly nymph Baetis rhodani. We also investigated alterations in microhabitat use and drift behaviour of B. rhodani in the presence of Gammarus, and indirect predatory interactions with juvenile Atlantic salmon, Salmo salar. 2. In trials with single predators and prey, B. rhodani survival was significantly lower when Gammarus were free to interact with nymphs as than when Gammarus were isolated from them. The invader G. pulex reduced the survival of B. rhodani more rapidly than did the native G. d. celticus. Both Gammarus spp. were active predators. 3. In `patch' experiments, B. rhodani survival was significantly lower both when G. pulex and G. d. celticus were present, although the effect of the two Gammarus species did not differ. Again, active predation of nymphs by Gammarus was observed. Significantly more nymphs occurred on the top and sides of a tile, and per capita drifts were significantly higher, when Gammarus were present. Baetis rhodani per capita drift was also significantly higher in the presence of the introduced G. pulex than with the native G. d. celticus. 4. Gammarus facilitated predation by salmon parr of B. rhodani by significantly increasing fish–nymph encounters on exposed gravel and in the drift. There were no differential effects of the two Gammarus spp. on fish –B. rhodani encounters or consumption. 5. We conclude that Gammarus as a predator can have lethal, nonlethal, direct and indirect effects in freshwaters. We stress the need for recognition of this predatory role when assigning Gammarus spp. to a `Functional Feeding Group'.