Intertidal molluscan and algal species richness around the UK coast

Geographically referenced databases of species records are becoming increasingly available. Doubts over the heterogeneous quality of the underlying data may restrict analyses of such collated databases. We partitioned the spatial variation in species richness of littoral algae and molluscs from the UK National Biodiversity Network database into a smoothed mesoscale component and a local component. Trend surface analysis (TSA) was used to define the mesoscale patterns of species richness, leaving a local residual component that lacked spatial autocorrelation. The analysis was based on 10 km grid squares with 115035 records of littoral algae (729 species) and 66879 records of littoral molluscs (569 species). The TSA identified variation in algal and molluscan species richness with a characteristic length scale of approximately 120 km. Locations of the most species-rich grid squares were consistent with the southern and western bias of species richness in the UK marine flora and fauna. The TSA also identified areas which showed significant changes in the spatial pattern of species richness: breakpoints, which correspond to major headlands along the south coast of England. Patterns of algal and molluscan species richness were broadly congruent. Residual variability was strongly influenced by proxies of collection effort, but local environmental variables including length of the coastline and variability in wave exposure were also important. Relative to the underlying trend, local species richness hotspots occurred on all coasts. While there is some justification for scepticism in analyses of heterogeneous datasets, our results indicate that the analysis of collated datasets can be informative.

Patterns of Holocene relative sea level change in the North of Britain and Ireland

Temporal and spatial patterns of relative sea level (RSL) change in the North of Britain and Ireland during the Holocene are examined. Four episodes, each defined by marked changes in the RSL trend, are identified. Each episode is marked by a rise to a culminating shoreline followed by a fall. Episode HRSL-1 dates from the Younger Dryas to early in the Holocene; HRSL-2 to HRSL-4 occurred later in the Holocene. There is extensive evidence for each episode, and on this basis the spatial distribution of the altitude data for three culminating shorelines and a shoreline formed at the time of the Holocene Storegga Slide tsunami (ca 8110 ± 100 cal. BP) is analysed. Ordinary Kriging is used to determine the general pattern, following which Gaussian Trend Surface Analysis is employed. Recognising that empirical measurements of RSL change can be unevenly distributed spatially, a new approach is introduced which enables the developing pattern to be identified. The patterns for the most widely occurring shorelines were analysed and found to be similar and common centre and axis models were developed for all shorelines. The analyses described provide models of the spatial pattern of Holocene RSL change in the area between ca 8100 cal. BP and ca 1000 cal. BP based on 2262 high resolution shoreline altitude measurements. These models fit the data closely, no shoreline altitude measurement lying more than −1.70 m or +1.82 m from the predicted value. The models disclose a similar pattern to a recently published Glacial Isostatic Adjustment model for present RSL change across the area, indicating that the overall spatial pattern of RSL change may not have varied greatly during the last ca 8000 years.

Are Alaskan trees found in locally more favourable sites in marginal areas?

Aim Species generally become rarer and more patchily distributed as the margins of their ranges are approached. We predicted that in such marginal sites, tree species would tend to occur where some key environmental factors are at particularly favourable levels, compensating in part for the low overall suitability of marginal sites.

Location The article considers the spatial distributions of trees in Southeast Alaska (the Alaskan 'panhandle').

Methods We quantified range marginality using spatial distributions of eight tree species across more than one thousand surveyed sites in Southeast Alaska. For each species we derived a site core/margin index using a three-dimensional trend surface generated from logistic regression on site coordinates. For each species, the relationships between the environmental factors slope, aspect and site marginality were then compared for occupied and unoccupied sets of sites.

Results We found that site slope is important for more Alaskan tree species than aspect. Three out of eight had a significant core/margin by occupied/unoccupied interaction, tending to be present in significantly shallower-sloped (more favourable) sites in the marginal areas than the simple core/margin trend predicted. For site aspect, one species had a significant interaction, selecting potentially more favourable northerly aspects in marginal areas. A finer-scale analysis based on the same data came to the same overall conclusions.

Conclusions There is evidence that several tree species in Alaska tend to occur in especially favourable sites in marginal areas. In these marginal areas, these species amplify habitat preferences shown in core areas.

Seasonal and diurnal variations in ultraviolet-B and ultraviolet-A irradiances at and below the sea surface at Helgoland (North Sea) over a 6-year period

Ultraviolet(UV) radiation at four wavelengths (305, 320, 340 and 380 nm) and photosynthetically active radiation (PAR) were measured from May 1994 to October 1999 using Biospherical UV radiometers. A surface reference sensor located on the roof of the Marine Station at Helgoland recorded values every 5 min, and an equivalent profiling underwater sensor was used for measurements in the sea at approximately monthly intervals. The ratio of 305-nm radiation to PAR varied seasonally, with a 14-fold increase from winter to summer. A much weaker seasonal trend (ca. 1.5-fold) was apparent in the ratio of 320-nm radiation to PAR, but there was no seasonal trend in the ratios of 340- or 380-nm radiation to PAR. The year-to-year variations in 305-nm radiation were also much greater relative to PAR than for the other UV wavelengths, but there was no evidence of a change in the 305 nm:PAR ratio over the study period. The ratios of both 305- and 320-nm radiation to PAR increased from dawn to midday, but those of 340- and 380-nm radiation were almost constant through the day, except shortly before sunrise and after sunset when the proportions of 340- and 380-nm radiation increased. Underwater measurements of PAR and UV suggest that the 1% depth for 305-nm radiation was little more than 1 m, but this estimate is valid only for summer and autumn because, in other seasons, few reliable readings for 305-nm radiation could be obtained underwater, and no attenuation coefficient could be calculated. The 1% depths recorded for the other UV wavelengths in the middle 6 months of the year were 2.0 m for 320 nm, 2.6 m for 340 nm and 4.6 m for 380 nm, compared with 12 m for PAR, but the attenuation of all wavebands increased sharply in October and remained higher until March. An analysis of the influence of sun angle, total column ozone concentration, the proportion of skylight, and cloud cover on the ratio of UV wavelengths to PAR in surface irradiance demonstrated that solar angle has a greater influence than ozone concentration on the irradiance at 305 nm, and that the typical occurrence of ozone

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces

The dissociative adsorption of N-2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

The importance of hydrogen's potential-energy surface and the strength of the forming R-H bond in surface hydrogenation reactions

An understanding of surface hydrogenation reactivity is a prevailing issue in chemistry and vital to the rational design of future catalysts. In this density-functional theory study, we address hydrogenation reactivity by examining the reaction pathways for N+H -> NH and NH+H -> NH2 over the close-packed surfaces of the 4d transition metals from Zr-Pd. It is found that the minimum-energy reaction pathway is dictated by the ease with which H can relocate between hollow-site and top-site adsorption geometries. A transition state where H is close to a top site reduces the instability associated with bond sharing of metal atoms by H and N (NH) (bonding competition). However, if the energy difference between hollow-site and top-site adsorption energies (Delta E-H) is large this type of transition state is unfavorable. Thus we have determined that hydrogenation reactivity is primarily controlled by the potential-energy surface of H on the metal, which is approximated by Delta E-H, and that the strength of N (NH) chemisorption energy is of less importance. Delta E-H has also enabled us to make predictions regarding the structure sensitivity of these reactions. Furthermore, we have found that the degree of bonding competition at the transition state is responsible for the trend in reaction barriers (E-a) across the transition series. When this effect is quantified a very good linear correlation is found with E-a. In addition, we find that when considering a particular type of reaction pathway, a good linear correlation is found between the destabilizing effects of bonding competition at the transition state and the strength of the forming N-H (HN-H) bond. (c) 2006 American Institute of Physics.

A density functional theory study of carbon monoxide oxidation on the Cu3Pt(111) alloy surface: Comparison with the reactions on Pt(111) and Cu(111)

Alloying metals is often used as an effective way to enhance the reactivity of surfaces. Aiming to shed light on the effect of alloying on reaction mechanisms, we carry out a comparative study of CO oxidation on Cu3Pt(111), Pt(111), and Cu(111) by means of density functional theory calculations. Alloying effects on the bonding sites and bonding energies of adsorbates, and the reaction pathways are investigated. It is shown that CO preferentially adsorbs on an atop site of Pt and O preferentially adsorbs on a fcc hollow site of three Cu atoms on Cu3Pt(111). It is also found that the adsorption energies of CO (or O-a) decreases on Pt (or Cu) on the alloy surface with respect to those on pure metals. More importantly, having identified the transition states for CO oxidation on those three surfaces, we found an interesting trend for the reaction barrier on the three surfaces. Similar to the adsorption energies, the reaction barrier on Cu3Pt possesses an intermediate value of those on pure Pt and Cu metals. The physical origin of these results has been analyzed in detail. (C) 2001 American Institute of Physics.

Monitoring a toxic bloom of Alexandrium minutum using novel microarray and multiplex surface plasmon resonance biosensor technology

Blooms of Alexandrium occur annually during the summer months in the North Channel of Cork Harbour on the south coast of Ireland. This study monitored an extensive bloom of the toxin producing Alexandrium minutum during the summer of 2011 with the use of the MIDTAL (Microarrays for the Detection of Toxic Algae) microarray and a prototype multiplex surface plasmon resonance (multi SPR) biosensor. Microarray signal intensities and toxin results from three testing platforms of the prototype multi SPR biosensor, commercial (CER) enzyme-linked immunosorbent assay (ELISA) and high performance liquid chromatography (HPLC) were compared against light microscopy counts. The main aim was to demonstrate the use of these methodologies to support national monitoring agencies by providing a faster and more accurate means of identifying and quantifying the harmful phytoplankton community and their toxins in natural water samples. Both the microarray signals and multi SPR biosensor results followed a significant trend with light microscopy results and both techniques indicated detection limits of <4000 cells of A. minutum in natural seawater samples.

An understanding and implications of the coverage of surface free sites in heterogeneous catalysis

The crucial roles of the coverage of surface free sites in determining catalytic activity trend are quantitatively addressed with the help of density functional theory and microkinetics. First, by analyzing activity trends of NO oxidation catalyzed by Ru, Rh, Pd, Os, Ir, and Pt surfaces with full kinetic considerations, we identify that the activity trend is in general determined by the competition between the reaction barrier and the coverage of surface free sites. Second, since the dissociation of many important molecules, such as the dissociation of N(2), O(2), and CO, follows the same Bronsted-Evans-Polanyi relationship, the coverage of surface free sites is usually a decisive term that affects the overall activity. Third, an equation is derived for the coverage of surface free sites and it is found that the coverage of surface free sites contains not only all the key thermodynamic parameters but also all the kinetic properties in the catalytic system. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3140202]

Time-lapse monitoring of climate effects on earthworks using surface waves

The UK’s transportation network is supported by critical geotechnical assets (cuttings/embankments/dams) that require sustainable, cost-effective management, while maintaining an appropriate service level to meet social, economic, and environmental needs. Recent effects of extreme weather on these geotechnical assets have highlighted their vulnerability to climate variations. We have assessed the potential of surface wave data to portray the climate-related variations in mechanical properties of a clay-filled railway embankment. Seismic data were acquired bimonthly from July 2013 to November 2014 along the crest of a heritage railway embankment in southwest England. For each acquisition, the collected data were first processed to obtain a set of Rayleigh-wave dispersion and attenuation curves, referenced to the same spatial locations. These data were then analyzed to identify a coherent trend in their spatial and temporal variability. The relevance of the observed temporal variations was also verified with respect to the experimental data uncertainties. Finally, the surface wave dispersion data sets were inverted to reconstruct a time-lapse model of S-wave velocity for the embankment structure, using a least-squares laterally constrained inversion scheme. A key point of the inversion process was constituted by the estimation of a suitable initial model and the selection of adequate levels of spatial regularization. The initial model and the strength of spatial smoothing were then kept constant throughout the processing of all available data sets to ensure homogeneity of the procedure and comparability among the obtained VS sections. A continuous and coherent temporal pattern of surface wave data, and consequently of the reconstructed VS models, was identified. This pattern is related to the seasonal distribution of precipitation and soil water content measured on site.