Understanding the Optimal Adsorption Energies for Catalyst Screening in Heterogeneous Catalysis

The fundamental understanding of the activity in heterogeneous catalysis has long been the major subject in chemistry. This paper shows the development of a two-step model to understand this activity. Using the theory of chemical potential kinetics with Bronsted-Evans-Polanyi relations, the general adsorption energy window is determined from volcano curves, using which the best catalysts can be searched. Significant insights into the reasons for catalytic activity are obtained.

Application of heterogeneous catalysts prepared by mechanochemical synthesis

Mechanochemical synthesis has the potential to provide more sustainable preparative routes to catalysts than the current multistep solvent-based routes. In this review, the mechanochemical synthesis of catalysts is discussed, with emphasis placed on catalysts for environmental, energy and chemical synthesis applications. This includes the formation of mixed-metal oxides as well as the process of dispersing metals onto solid supports. In most cases the process involves no solvent. Encouragingly, there are several examples where the process is advantageous compared with the more normal solvent-based methods. This can be because of process cost or simplicity, or, notably, where it provides more active/selective catalysts than those made by conventional wet chemical methods. The need for greater, and more systematic, exploration of this currently unconventional approach to catalyst synthesis is highlighted.

Physicochemical tolerance, habitat use and predation are drivers of patterns of coexistence and exclusion among invasive and resident amphipods

1. Patterns of coexistence and exclusion among resident and invading species in freshwaters may be generated by direct biotic interactions well as by indirect interactions with the broader abiotic and biotic environments. The North American ‘shrimp’ Crangonyx pseudogracilis (Crustacea: Amphipoda) is invasive in Europe where it forms complex patterns of apparent exclusion and coexistence with resident Gammarus spp. amphipods. Using a comprehensive integrated approach, we investigated the potential biotic and interacting abiotic factors driving these distribution patterns.
2. A 2009 of 69 sites revealed that of 56 river sites containing amphipods only 6 contained C. pseudogracilis and these always co-occurred with Gammarus spp.. In contrast, C. pseudogracilis was the only species present in the 12 ponds/reservoirs containing amphipods.
3. Field transplant experiments in ponds and laboratory oxygen tolerance experiments revealed that C. pseudogracilis tolerates physicochemical regimes which Gammarus spp. are incapable of surviving.
4. River microhabitat sampling showed C. pseudogracilis dominating in slower, more pooled and macrophyte-dense patches, while Gammarus spp. were dominant in faster, more riffled areas.
5. Field bioassays indicated that predation of C. pseudogracilis by Gammarus spp. may be frequent in patches of rivers if/when the species meet.
6. River drift sampling revealed that C. pseudogracilis was greatly underrepresented in night/day drift relative to the Gammarus spp.. Laboratory studies showed C. pseudogracilis to be more photophobic and less active than Gammarus spp., both behaviours potentially contributing to low drift prevalence and consequent reduced exposure to shared drift predators.
7. These interacting factors may ultimately contribute to the coexistence, exclusion and relative distributions of C. pseudogracilis and Gammarus spp.. The former is potentially subject to intense predation from the latter if they encounter one another in the same microhabitat. However, with C. pseudogracilis being more physicochemically tolerant and displaying different habitat utilisation patterns than the Gammarus spp. in respect of the benthos and drift, such encounters are probably minimised. Hence C. pseudogracilis can persist in the same sites with the Gammarus spp., albeit in different microhabitats.

Habitat simplification increases the impact of a freshwater invasive fish

Biodiversity continues to decline at a range of spatial scales and there is an urgent requirement to understand how multiple drivers interact in causing such declines. Further, we require methodologies that can facilitate predictions of the effects of such drivers in the future. Habitat degradation and biological invasions are two of the most important threats to biodiversity and here we investigate their combined effects, both in terms of understanding and predicting impacts on native species. The predatory largemouth bass Micropterus salmoides is one of the World’s Worst Invaders, causing declines in native prey species, and its introduction often coincides with habitat simplification. We investigated the predatory functional response, as a measure of ecological impact, of juvenile largemouth bass in artificial vegetation over a range of habitat complexities (high, intermediate, low and zero). Prey, the female guppy Poecilia reticulata, were representative of native fish. As habitats became less complex, significantly more prey were consumed, since, even although attack rates declined, reduced handling times resulted in higher maximum feeding rates by bass. At all levels of habitat complexity, bass exhibited potentially population destabilising Type II functional responses, with no emergence of more stabilising Type III functional responses as often occurs in predator-prey relationships in complex habitats. Thus, habitat degradation and simplification potentially exacerbate the impact of this invasive species, but even highly complex habitats may ultimately not protect native species. The utilisation of functional responses under varying environmental contexts provides a method for the understanding and prediction of invasive species impacts.

Coupling ground and airborne geophysical data with upscaling techniques for regional groundwater modeling of heterogeneous aquifers: Case study of a sedimentary aquifer intruded by volcanic dykes in Northern Ireland

In highly heterogeneous aquifer systems, conceptualization of regional groundwater flow models frequently results in the generalization or negligence of aquifer heterogeneities, both of which may result in erroneous model outputs. The calculation of equivalence related to hydrogeological parameters and applied to upscaling provides a means of accounting for measurement scale information but at regional scale. In this study, the Permo-Triassic Lagan Valley strategic aquifer in Northern Ireland is observed to be heterogeneous, if not discontinuous, due to subvertical trending low-permeability Tertiary dolerite dykes. Interpretation of ground and aerial magnetic surveys produces a deterministic solution to dyke locations. By measuring relative permeabilities of both the dykes and the sedimentary host rock, equivalent directional permeabilities, that determine anisotropy calculated as a function of dyke density, are obtained. This provides parameters for larger scale equivalent blocks, which can be directly imported to numerical groundwater flow models. Different conceptual models with different degrees of upscaling are numerically tested and results compared to regional flow observations. Simulation results show that the upscaled permeabilities from geophysical data allow one to properly account for the observed spatial variations of groundwater flow, without requiring artificial distribution of aquifer properties. It is also found that an intermediate degree of upscaling, between accounting for mapped field-scale dykes and accounting for one regional anisotropy value (maximum upscaling) provides results the closest to the observations at the regional scale.

SHEPARD: Scheduling on heterogeneous platforms using application resource demands

Heterogeneous computing technologies, such as multi-core CPUs, GPUs and FPGAs can provide significant performance improvements. However, developing applications for these technologies often results in coupling applications to specific devices, typically through the use of proprietary tools. This paper presents SHEPARD, a compile time and run-time framework that decouples application development from the target platform and enables run-time allocation of tasks to heterogeneous computing devices. Through the use of special annotated functions, called managed tasks, SHEPARD approximates a task's performance on available devices, and coupled with the approximation of current device demand, decides which device can satisfy the task with the lowest overall execution time. Experiments using a task parallel application, based on an in-memory database, demonstrate the opportunity for automatic run-time task allocation to achieve speed-up over a static allocation to a single specific device. © 2014 IEEE.

Power Modeling and Capping for Heterogeneous ARM/FPGA SoCs

Low-power processors and accelerators that were originally designed for the embedded systems market are emerging as building blocks for servers. Power capping has been actively explored as a technique to reduce the energy footprint of high-performance processors. The opportunities and limitations of power capping on the new low-power processor and accelerator ecosystem are less understood. This paper presents an efficient power capping and management infrastructure for heterogeneous SoCs based on hybrid ARM/FPGA designs. The infrastructure coordinates dynamic voltage and frequency scaling with task allocation on a customised Linux system for the Xilinx Zynq SoC. We present a compiler-assisted power model to guide voltage and frequency scaling, in conjunction with workload allocation between the ARM cores and the FPGA, under given power caps. The model achieves less than 5% estimation bias to mean power consumption. In an FFT case study, the proposed power capping schemes achieve on average 97.5% of the performance of the optimal execution and match the optimal execution in 87.5% of the cases, while always meeting power constraints.

Range expansion and comparative habitat use of insular, congeneric lagomorphs: invasive European hares Lepus europaeus and endemic Irish hares Lepus timidus hibernicus

The European hare (Lepus europaeus) has declined throughout its native range but invaded numerous regions where it has negatively impacted native wildlife. In southern Sweden, it replaces the native mountain hare (L. timidus) through competition and hybridisation. We investigated temporal change in the invasive range of the European hare in Ireland, and compared its habitat use with the endemic Irish hare (L. timidus hibernicus). The range of the European hare was three times larger and its core range twice as large in 2012–2013 than in 2005. Its rate of radial range expansion was 0.73 km year−1 with its introduction estimated to have occurred ca. 1970. Both species utilised improved and rough grasslands and exhibited markedly similar regression coefficients with almost every land cover variable examined. Irish hares were associated with low fibre and high sugar content grass (good quality grazing) whilst the invader had a greater tolerance for low quality forage. European hares were associated with habitat patch edge density, suggesting it may be more suited to using hedgerows as diurnal resting sites than the Irish hare. Consequently, the invader had a wider niche breadth than the native but their niche overlap was virtually complete. Given the impact of the European hare on native species elsewhere, and its apparent pre-adaption for improved grasslands interspersed with arable land (a habitat that covers 70 % of Ireland), its establishment and range expansion poses a significant threat to the ecological security of the endemic Irish hare, particularly given their ecological similarities.

Stochastic Analysis of Saltwater Intrusion in Heterogeneous Aquifers using Local Average Subdivision

This study investigates the effects of ground heterogeneity, considering permeability as a random variable, on an intruding SW wedge using Monte Carlo simulations. Random permeability fields were generated, using the method of Local Average Subdivision (LAS), based on a lognormal probability density function. The LAS method allows the creation of spatially correlated random fields, generated using coefficients of variation (COV) and horizontal and vertical scales of fluctuation (SOF). The numerical modelling code SUTRA was employed to solve the coupled flow and transport problem. The well-defined 2D dispersive Henry problem was used as the test case for the method. The intruding SW wedge is defined by two key parameters, the toe penetration length (TL) and the width of mixing zone (WMZ). These parameters were compared to the results of a homogeneous case simulated using effective permeability values. The simulation results revealed: (1) an increase in COV resulted in a seaward movement of TL; (2) the WMZ extended with increasing COV; (3) a general increase in horizontal and vertical SOF produced a seaward movement of TL, with the WMZ increasing slightly; (4) as the anisotropic ratio increased the TL intruded further inland and the WMZ reduced in size. The results show that for large values of COV, effective permeability parameters are inadequate at reproducing the effects of heterogeneity on SW intrusion.

Experimental Investigation of Transient Saltwater Intrusion in Heterogeneous Porous Media

A 2D sandbox style experiment was developed to compare the results of numerical modelling to physical testing for saltwater intrusion in homogeneous and heterogeneous aquifers. The sandbox consisted of a thin central viewing chamber filled with glass beads of varying diameters (780μm, 1090μm and 1325μm) under fully saturated conditions. Dyed saltwater (SW) was introduced at the side boundary and a head difference imposed across the porous media. Images of the SW wedge were recorded at intervals in order to assess the suitability of the numerical models predictions of transient SW intrusion. Numerical modelling of the experimental cases were simulated using SUTRA. Two main parameters were chosen to express the condition of the intruding SW wedge at each recorded time step; the toe penetration length (TL) and the width of the mixing zone (WMZ). The WMZ was larger under transient conditions in the heterogeneous case, while the TL was longer for the homogeneous case. The increased variability in the flow field fo the heterogeneous case resulted in increased dispersion, and thus, increased WMZ.

Supplementary feeding increases Common Buzzard Buteo buteo productivity but only in poor-quality habitat

Temporal heterogeneity in the effects of food supply during the breeding season on the productivity of the Common Buzzard Buteo buteo was investigated in a supplementary feeding experiment. Pairs were fed artificially (1) before egg-laying, (2) after chicks hatched and (3) continuously throughout the season, and compared with (4) unfed controls. Pairs fed before egg-laying had marginally larger clutches than those not fed, but lay date, egg volume and weight, brood size and hatching success were unaffected. Territorial quality had far greater effects, with pairs nesting in low-quality habitats (bog, scrub and semi-natural grassland) laying later and having lower hatching success, smaller broods and fewer fledglings than those in more productive agricultural landscapes. Supplementary feeding after egg hatching neutralized the negative effect of poor habitat, resulting in fed birds having significantly more fledglings. This study emphasizes the importance of food availability when provisioning chicks in suboptimal habitats and has implications for the success of diversionary feeding in reducing game losses to Buzzards.

Scyphozoan jellyfish provide short-term reproductive habitat for hyperiid amphipods in a temperate near-shore environment

Hyperiid amphipods (Order Amphipoda, Suborder Hyperiidea) are known to infest gelatinous zooplankton. However, the temporal backdrop to these associations is less clear, given that data are often gathered during discrete sampling events rather than over time. In general, hyperiids are considered to be pelagic: however, for individuals associated with metagenic jellyfishes in temperate shallow shelf seas, this may not always be the case, as the majority of their gelatinous hosts are present in the water column from spring to the onset of autumn. Here, we explored the temporal patterns of colonisation and overall duration of the association between Hyperia galba and 3 scyphozoan jellyfish species (Aurelia aurita, Cyanea capillata and C. lamarckii) in a temperate coastal system (Strangford Lough, Northern Ireland) during 2010 and 2012. Concomitantly, we used carbon and nitrogen stable isotope ratios to examine whether hyperiid infestation represented a permanent association with their host or was part of a more complex life history. We found that jellyfish were colonised by H. galba ca. 2 mo after they are first observed in the lough and that H. galba reached 100% prevalence in the different jellyfish species shortly before the medusae of each species disappeared from the water column. It is possible that some jellyfish overwintered in deeper water, prolonging the association between H. galba and their hosts. However, all the medusae sampled during the spring and early summer (whether they were newly emerged or had overwintered from the previous season) were not infected with hyperiids, suggesting that such behaviour was uncommon or that individuals had become dissociated from their host during the winter. Further evidence of temporary association came from stable isotope data, where δ13C and δ15N isotope ratios were indicative of feeding outside of their host prior to jellyfish colonisation. In combination, these findings suggest alternating habitat associations for H. galba, with the amphipods spending the majority of the year outside of the 3 scyphozoan species considered here.

Spatio-temporal Change in Crowned (Propithecus coronatus) and Decken’s Sifaka (Propithecus deckenii) Habitat in the Mahavavy-Kinkony Wetland Complex, Madagascar.

The crowned sifaka (Propithecus coronatus) and Decken’s sifaka (Propithecus deckenii) are Endangered lemurs endemic to west and central Madagascar. Both have suffered habitat loss and fragmentation throughout their ranges. The goal
of this study, conducted in the Mahavavy-Kinkony Wetland Complex (MKWC) in northwestern Madagascar, was to assess the effects of historical change in the species’ habitats, and to model the potential impact of further land-use change on their habitats. The IDRISI Andes Geographical Information System and image-processing software was used for satellite-image classifiation, and the Land Change Modeler was used to compare the natural habitat of the species from 1973 to 2005, and to predict available habitat for 2050. We analyzed two forests in the MKWC occupied by P. coronatus (Antsilaiza and Anjohibe), and three forests occupied by P. deckenii (Tsiombikibo, Marofandroboka and Andohaomby). The two forests occupied by P. coronatus contracted during the period 1949–1973, but then expanded to exceed their 1949 area by 28% in 2005. However, the land change model predicted that they will contract again to match their 1949 area by 2050, and will again lose their corridor connection, meaning that the conservation gains for this species in the complex are at risk of being reversed. The three forests occupied by P. deckenii have declined in area steadily since 1949, losing 20% of their original area by 2005, and are predicted to lose a further 15% of their original area by 2050. Both species are therefore at risk of becoming even more threatened if land-use change continues within the complex. Improved conservation of the remaining forest is recommended to avoid further loss, as well as ecological restoration and reforestation to promote connectivity between the forests. A new strategy for controlling agriculture and forest use is required in order to avoid further destruction of the forest.