SpaciMS: spatial and temporal operando resolution of reactions within catalytic monoliths

Monolithic catalysts are widely used as structured catalysts, especially in the abatement of pollutants. Probing what happens inside these monoliths during operation is, therefore, vital for modelling and prediction of the catalyst behavior. SpaciMS is a spatially resolved capillary-inlet mass spectroscopy system allowing for the generation of spatially resolved maps of the reactions within monoliths. In this study SpaciMS results combined with 3D CFD modelling demonstrate that SpaciMS is a highly sensitive and minimally invasive technique that can provide reaction maps as well as catalytic temporal behavior. Herein we illustrate this by examining kinetic oscillations during a CO oxidation reaction over a Pt/Rh on alumina catalyst supported on a cordierite monolith. These oscillations were only observed within the monolith by SpaciMS between 30 and 90% CO conversion. Equivalent experiments performed in a plug-flow reactor using this catalyst in a crushed form over a similar range of reaction conditions did not display any oscillations demonstrating the importance of intra monolith analysis. This work demonstrates that the SpaciMS offers an accurate and comprehensive picture of structured catalysts under operation.

Spatial characterization of salt accumulation in early stage limestone weathering using probe permeametry

This research characterizes the weathering of natural building stone using an unsteady-state portable probe permeameter. Variations between the permeability properties of fresh rock and the same rocks after the early stages of a salt weathering simulation are used to examine the effects of salt accumulation on spatial variations in surface rock permeability properties in two limestones from Spain. The Fraga and Tudela limestones are from the Ebro basin and are of Miocene age. Both stone types figure largely in the architectural heritage of Spain and, in common with many other building limestones, they are prone to physical damage from salt crystallization in pore spaces. To examine feedbacks associated with salt accumulation during the early stages of this weathering process, samples of the two stone types were subjected to simulated salt weathering under laboratory conditions using magnesium sulphate and sodium chloride at concentrations of 5% and 15%. Permeability mapping and statistical analysis (aspatial statistics and spatial prediction) before and after salt accumulation are used to assess changes in the spatial variability of permeability and to correlate these changes with salt movement, porosity change, potential rock deterioration and textural characteristics. Statistical analyses of small-scale permeability measurements are used to evaluate the drivers for decay and hence aid the prediction of the weathering behaviour of the two limestones.

Distance between home and work: A multilevel analysis of individual workers, neighbourhoods, and employment sites in Northern Ireland

Abstract. We explore the distances between home and work for employees at twenty-eight different employment sites across Northern Ireland. Substantively, this is important for better understanding the geography of labour catchments. Methodologically, with data on the distances between place of residence (566 wards) and place of work for some 15 000 workers, and the use of multilevel modelling (MLM), the analysis adds to the evidence derived from other census-based and survey-based studies. Descriptive analysis is supplemented with MLM that simultaneously explores individual, neighbourhood, and site variations in travel-to-work patterns using hierarchical and cross-classified model specifications, including individual and ecological predictor variables (and their cross-level interactions). In doing so we apportion variability to different levels and spatial contexts, and also outline the factors that shape spatial mobility. We find, as expected, that factors such as gender and occupation influence the distance between home and work, and also confirm the importance of neighbourhood characteristics (such as population density observed in ecological analyses at ward level) in shaping individual outcomes, with major differences found between urban and rural locations. Beyond this, the analysis of variability also points to the relative significance of residential location, with less individual variability in travel-to-work distance between workers within wards than within employment sites. We conclude by suggesting that, whilst some general ‘rules’ about the factors that shape labour catchments are possible (eg workers in rural areas and in higher occupations travel further than others), the complex variability between places highlighted by the MLM analysis illustrates the salience of place-specific uniqueness.

A new algorithm for spectral and spatial reconstruction of proton beams from dosimetric measurements

We report on a new algorithm developed for the dosimetric analysis of broad-spectrum, multi-MeV laser-accelerated proton beams. The algorithm allows the reconstruction of the proton beam spectrum from radiochromic film data. This processing technique makes dosimetry measurements a viable alternative to the use of track detectors for spatially and spectrally resolved proton beam analysis. (C) 2003 Elsevier B.V. All rights reserved.

Spatio-temporal analysis of DNA damage repair using the X-ray microbeam

Cellular response to radiation damage is made by a complex network of pathways and feedback loops whose spatiotemporal organization is still unclear despite its decisive role in determining the fate of the damaged cell. The single-cell approach and the high spatial resolution offered by microbeams provide the perfect tool to study and quantify the dynamic processes associated with the induction and repair of DNA damage. The soft X-ray microbeam has been used to follow the development of radiation induced foci in live cells by monitoring their size and intensity as a function of dose and time using yellow fluorescent protein (YFP) tagging techniques. Preliminary data indicate a delayed and linear rising of the intensity signal indicating a slow kinetic for the accumulation of DNA repair protein 53BP1. A slow and limited foci diffusion has also been observed. Further investigations are required to assess whatever such diffusion is consistent with a random walk pattern or if it is the result of a more structured lesion processing phenomenon. In conclusion, our data indicates that the use of microbeams coupled to live cell microscopy represent a sophisticated approach for visualizing and quantifying the dynamics changes of DNA proteins at the damaged sites.

Spatial Mobility Intentions, the Labour Market and Incapacity Benefit Claimants Evidence from Northern Ireland

The paper analyses the work-related spatial mobility intentions of incapacity benefit (IB) claimants in Northern Ireland using a new survey dataset. Greater understanding of the prospective mobility of benefit claimants contributes to debates about employability, inclusion in the labour market and arguments about spatial mismatch. The analysis finds that IB claimants are not markedly less mobile than other population groups; that mobility is shaped by age, level of qualification, illness type, ability to drive and motivation; and that geography is important in several ways. The paper concludes by arguing that limited spatial mobility is a good indicator of disadvantage and that spatial mobility should be placed nearer the centre of the design and delivery of labour market policy

Residential segregation in Northern Ireland in 2001: assessing the value of exploring spatial variations

Segregation measures have been applied in the study of many societies, and traditionally such measures have been used to assess the degree of division between social and cultural groups across urban areas, wider regions, or perhaps national areas. The degree of segregation can vary substantially from place to place even within very small areas. In this paper the substantive concern is with religious/political segregation in Northern Ireland—particularly the proportion of Protestants (often taken as an indicator of those who wish to retain the union with Britain) to Catholics (often taken as an indicator of those who favour union with the Republic of Ireland). Traditionally, segregation is measured globally—that is, across all units in a given area. A recent trend in spatial data analysis generally, and in segregation analysis specifically, is to assess local features of spatial datasets. The rationale behind such approaches is that global methods may obscure important spatial variations in the property of interest, and thus prevent full use of the data. In this paper the utility of local measures of residential segregation is assessed with reference to the religious/political composition of Northern Ireland. The paper demonstrates marked spatial variations in the degree and nature of residential segregation across Northern Ireland. It is argued that local measures provide highly useful information in addition to that provided in maps of the raw variables and in standard global segregation measures.

Population dynamics of the liver fluke, Fasciola hepatica: the effect of time and spatial separation on the genetic diversity of fluke populations in the Netherlands

An evaluation of the genetic diversity within Fasciola hepatica (liver fluke) may provide an insight into its potential to respond to environmental changes, such as anthelmintic use or climate change. In this study, we determined the mitochondrial DNA haplotypes of >400 flukes from 29 individual cattle, from 2 farms in the Netherlands, as an exemplar of fasciolosis in a European context. Analysis of this dataset has provided us with a measure of the genetic variation within infrapopulations (individual hosts) and the diversity between infrapopulations within a herd of cattle. Temporal sampling from one farm allowed for the measurement of the stability of genetic variation at a single location, whilst the comparison between the two farms provided information on the variation in relation to distance and previous anthelmintic regimes. We showed that the liver fluke population in this region is predominantly linked to 2 distinct clades. Individual infrapopulations contain a leptokurtic distribution of genetically diverse flukes. The haplotypes present on a farm have been shown to change significantly over a relatively short time-period.

The Architecture of Home in Cairo: Socio-Spatial Practice of the Hawari's Everyday Life

The hawari of Cairo - narrow non-straight alleyways - are the basic urban units that have formed the medieval city since its foundation back in 969 AD. Until early in the C20th, they made up the primary urban divisions of the city and were residential in nature. Contemporary hawari, by contrast, are increasingly dominated by commercial and industrial activity. This medieval urban maze of extremely short, broken, zigzag streets and dead ends are defensible territories, powerful institutions, and important social systems. While the hawari have been studied as an exemplar for urban structure of medieval Islamic urbanism, and as individual building typologies, this book is the first to examine in detail the socio-spatial practice of the architecture of home in the city. It investigates how people live, communicate and relate to each other within their houses or shared spaces of the alleys, and in doing so, to uncover several new socio-spatial dimensions and meanings in this architectural form.

In an attempt to re-establish the link between architecture past and present, and to understand the changing social needs of communities, this book uncovers the notion of home as central to understand architecture in such a city with long history as Cairo. It firstly describes the historical development of the domestic spaces (indoor and outdoor), and provides an inclusive analysis of spaces of everyday activities in the hawari of old Cairo. It then broadens its analysis to other parts of the city, highlighting different customs and representations of home in the city at large. Cairo, in the context of this book, is represented as the most sophisticated urban centre in the Middle East with different and sometimes contrasting approaches to the architecture of home, as a practice and spatial system.

In order to analyse the complexity and interconnectedness of the components and elements of the hawari as a 'collective home', it layers its narratives of architectural and social developments as a domestic environment over the past two hundred years, and in doing so, explores the in-depth social meaning and performance of spaces, both private and public.

The spatial distribution of Holocene cryptotephras in north-west Europe since 7 ka: implications for understanding ash fall events from Icelandic eruptions

We present distribution maps for all cryptotephras (distal volcanic ash layers) younger than 7 ka that have been reported from three or more lakes or peatlands in north-west Europe. All but one of the tephras originates from Iceland; the exception has been attributed to Jan Mayen. We find strong spatial patterning in tephra occurrence at the landscape scale; most, but not all of the tephra occurrences are significantly spatially clustered, which likely reflects atmospheric and weather patterns at the time of the eruptions. Contrary to expectations based on atmospheric modelling studies, tephras appear to be at least as abundant in Ireland and northern Scotland as in Scandinavia. Rhyolitic and other felsic tephras occur in lakes and peatlands throughout the study region, but andesitic and basaltic tephras are largely restricted to lake sites in the Faroe Islands and Ireland. Explanations of some of these patterns will require further research on the effects of different methodologies for locating and characterizing cryptotephras. These new maps will help to guide future investigations in tephrochronology and volcanic hazard analysis.

Blue luminous stars in nearby galaxies: Quantitative spectral analysis of M33 B-type supergiant stars

We present the detailed spectral analysis of a sample of M33 B-type supergiant stars, aimed at the determination of their fundamental parameters and chemical composition. The analysis is based on a grid of non-LTE metal line-blanketed model atmospheres including the effects of stellar winds and spherical extension computed with the code FASTWIND. Surface abundance ratios of C, N, and O are used to discuss the chemical evolutionary status of each individual star. The comparison of observed stellar properties with theoretical predictions of massive star evolutionary models shows good agreement within the uncertainties of the analysis. The spatial distribution of the sample allows us to investigate the existence of radial abundance gradients in the disk of M33. The comparison of stellar and H II region O abundances ( based on direct determinations of the electron temperature of the nebulae) shows good agreement. Using a simple linear radial representation, the stellar oxygen abundances result in a gradient of -0.0145 +/- 0.005 dex arcmin(-1) (or -0.06 +/- 0.02 dex kpc(-1)) up to a distance equal to similar to 1.1 times the isophotal radius of the galaxy. A more complex representation cannot be completely discarded by our stellar sample. The stellar Mg and Si abundances follow the trend displayed by O abundances, although with shallower gradients. These differences in gradient slope cannot be explained at this point. The derived abundances of the three alpha-elements yield solar metallicity in the central regions of the disk of M33. A comparison with recent planetary nebula data from Magrini and coworkers indicates that the disk of M33 has not suffered from a significant O enrichment in the last 3 Gyr.

A Monte Carlo model of DNA double-strand break clustering and rejoining kinetics for the analysis of pulsed-field gel electrophoresis data

In studies of radiation-induced DNA fragmentation and repair, analytical models may provide rapid and easy-to-use methods to test simple hypotheses regarding the breakage and rejoining mechanisms involved. The random breakage model, according to which lesions are distributed uniformly and independently of each other along the DNA, has been the model most used to describe spatial distribution of radiation-induced DNA damage. Recently several mechanistic approaches have been proposed that model clustered damage to DNA. In general, such approaches focus on the study of initial radiation-induced DNA damage and repair, without considering the effects of additional (unwanted and unavoidable) fragmentation that may take place during the experimental procedures. While most approaches, including measurement of total DNA mass below a specified value, allow for the occurrence of background experimental damage by means of simple subtractive procedures, a more detailed analysis of DNA fragmentation necessitates a more accurate treatment. We have developed a new, relatively simple model of DNA breakage and the resulting rejoining kinetics of broken fragments. Initial radiation-induced DNA damage is simulated using a clustered breakage approach, with three free parameters: the number of independently located clusters, each containing several DNA double-strand breaks (DSBs), the average number of DSBs within a cluster (multiplicity of the cluster), and the maximum allowed radius within which DSBs belonging to the same cluster are distributed. Random breakage is simulated as a special case of the DSB clustering procedure. When the model is applied to the analysis of DNA fragmentation as measured with pulsed-field gel electrophoresis (PFGE), the hypothesis that DSBs in proximity rejoin at a different rate from that of sparse isolated breaks can be tested, since the kinetics of rejoining of fragments of varying size may be followed by means of computer simulations. The problem of how to account for background damage from experimental handling is also carefully considered. We have shown that the conventional procedure of subtracting the background damage from the experimental data may lead to erroneous conclusions during the analysis of both initial fragmentation and DSB rejoining. Despite its relative simplicity, the method presented allows both the quantitative and qualitative description of radiation-induced DNA fragmentation and subsequent rejoining of double-stranded DNA fragments. (C) 2004 by Radiation Research Society.

Confined site construction: An empirical analysis of factors impacting health and safety management

Purpose – The purpose of this paper is to identify, clarify and tabulate the various managerial issues encountered, to aid in the management of the complex health and safety concerns which occur within a confined construction site environment.

Design/methodology/approach – This is achieved through conducting extensive qualitative and qualitative research in the form of case studies, interviews and questionnaire survey.

Findings – The leading managerial issues in the management of health and safety on a confined construction site are found to be: “Difficulty to move materials around site safely”; “Lack of adequate room for the effective handling of materials”; “Difficulty in ensuring site is tidy and all plant and materials are stored safely”; “Close proximity of individuals to operation of large plant and machinery”; and joint fifth “Difficulty in ensuring proper arrangement and collection of waste materials on-site” along with “Difficulty in controlling hazardous materials and equipment on site”.

Practical implications – The resulting implication for practice of these results can be summarised by identifying that with sustained development of urban centres on a global scale, coupled with the increasing complexity of architectural designs, the majority of on-site project management professionals are faced with the onerous task of completing often intricate designs within a limited spatial environment, under strict health and safety parameters.

Originality/value – The subsequent value of the findings are such that just as on-site management professionals successfully identify the various managerial issues highlighted, the successful management of health and safety on a confined construction site is attainable.

Heritability of the spatial distribution and peak density of macular pigment:a classical twin study

Purpose: To elucidate the heritability of peak density and spatial width of macular pigment (MP) using a Classical Twin Study.

Methods: Fundus autofluorescence images were obtained at 488?nm from 86 subjects or 43 twin pairs (21 monozygotic (MZ) and 22 dizygotic (DZ)) (27 male, 59 female) aged from 55 to 76 years (mean 62.2±5.3 years). The relative topographic distribution of MP was measured using a grey scale of intensity (0-255 units) in a 7° eccentricity around the fovea. Relative peak MP density (rPMPD) and relative spatial distribution of MP (rSDMP) were used as the main outcome measure in the statistical analysis.

Results: A significantly higher correlation was found within MZ pairs as compared with that within DZ pairs for rPMPD, (r=0.99, 95% confidence interval (95% CI) 0.93 to 1.00) and 0.22, 95% CI -0.34 to 0.71), respectively, suggesting strong heritability of this trait. When rSDMP was compared, there was no significant difference between the correlations within MZ pairs (r=0.48, 95% CI -0.02 to 0.83) and DZ pairs (r=0.63, 95% CI 0.32 to 0.83), thus rSDMP is unlikely to have a considerable heritable component. In addition, there was no difference between any MP parameter when normal maculae were compared with early age-related macular degeneration (AMD) (rPMPD 0.36 vs 0.34, t=1.18 P=0.243, rSDMP 1.75 vs 1.75, t=0.028 P=0.977).ConclusionsrPMPD is a strongly heritable trait whereas rSDMP has minimal genetic influence and a greater influence by environmental factors. The presence of macular changes associated with early AMD did not appear to influence any of these pigment parameters. © 2012 Macmillan Publishers Limited All rights reserved 0950-222X/12

A review of spatial and temporal variation in grey and common seal diet in the United Kingdom and Ireland

Knowledge about the diet of fish-eating predators is critical when evaluating conflicts with the fishing industry. Numerous primary studies have examined the diet of grey seals Halichoerus grypus and common seals Phoca vitulina in a bid to understand the ecology of these predators. However, studies of large-scale spatial and temporal variation in seal diet are limited. Therefore this review combines the results of seal diet studies published between 1980 and 2000 to examine how seal diet varies at a range of spatial and temporal scales. Our results revealed extensive spatial variation in gadiform, perciform and flatfish consumption, likely reflecting variation in prey availability. Flatfish and gadiform consumption varied between years, reflecting changes in fish assemblages as a consequence of factors such as varying fishing pressures, climate change and natural fluctuations in populations. Perciform and gadiform consumption varied seasonally: in addition there was a significant interaction between season and seal species, indicating that grey and common seals exhibited different patterns of seasonal variation in their consumption of Perciformes and Gadiformes. Multivariate analysis of grey seal diet revealed spatial variation at a much smaller scale, with different species dominating the diet in different areas. The existence of spatial and temporal variation in seal diet emphasizes that future assessments of the impact of seal populations should not be based on past or localized estimates of diet and highlights the need for up-to-date, site specific estimates of diet composition in the context of understanding and resolving seal/fisheries conflict. © 2012 Marine Biological Association of the United Kingdom.