A density functional theory study on the water formation at high coverages and the water effect in the Fischer-Tropsch synthesis

The O removal through water formation is an important process in the Fischer-Tropsch synthesis. In this study, both steps in water formation (O + H --> OH, OH + H --> H2O) are studied on the stepped Co(0001) at high coverages using density functional theory. We find the following. (i) In both O-O and O-OH co-adsorption systems, two transition states (TSs) were located for the O hydrogenation: in one TS, both O and H are on the same terrace, and in the other they are at the interface between the step edge and the terrace below. (ii) In both the O-O and O-OH co-adsorption systems, the O hydrogenation at the interface is easier (E-a = 0.32 eV in the O-O system, E-a = 1.10 eV in the O-OH system) than that on the same terrace (E-a = 1.49 eV in the O-O system, E-a = 1.80 eV in the O-OH system). (iii) In both the O-O and O-OH co-adsorption systems, only one TS for the OH hydrogenation was located, in which both OH and H are on the same terrace. (iv) Compared to the OH hydrogenation in the O-OH system (E-a = 1.46 eV), the reaction in the OH-OH system (E-a = 0.64 eV) is much easier. The barrier differences and the water effect on the Fischer-Tropsch synthesis are discussed. A possible route with low barriers for water formation is proposed.

The catalytic role of water in CO oxidation

Water, one of the most popular species in our planet, can play a catalytic role in many reactions, including reactions in heterogeneous catalysis. In a recent experimental work, Bergeld, Kasemo, and Chakarov demonstrated that water is able to promote CO oxidation under low temperatures (similar to200 K). In this study, we choose CO oxidation on Pt(111) in the presence of water as a model system to address the catalytic role of water for surface reactions in general using density functional theory. Many elementary steps possibly involved in the CO oxidation on Pt(111) at low temperatures have been investigated. We find the following. First, in the presence of water, the CO oxidation barrier is reduced to 0.33 eV (without water the barrier is 0.80 eV). This barrier reduction is mainly due to the H-bonding between the H in the H2O and the O at the transition state (TS), which stabilizes the TS. Second, CO can readily react with OH with a barrier of 0.44 eV, while COOH dissociation to produce CO2 is not easy (the barrier is 1.02 eV). Third, in the H2O+OH mixed phase, CO can be easily converted into CO2. It occurs through two steps: CO reacts with OH, forming COOH; and COOH transfers the H to a nearby H2O and, at the same time, an H in the H2O transfers to a OH, leading to CO2 formation. The reaction barrier of this process is 0.60 eV under CO coverage of 1/6 ML and 0.33 eV under CO coverage of 1/3 ML. The mechanism of CO oxidation at low temperatures is discussed. On the basis of our calculations, we propose that the water promotion effect can in general be divided into two classes: (i) By H-bonding between the H of H2O and an electron negative species such as the O in the reaction of CO+O+H2O-->CO2+H2O, H2O can stabilize the TS of the reaction and hence reduce the barrier. (ii) H2O first dissociates into H and OH and then OH or H participates directly in the reaction to induce new reaction mechanism with more favorable routes, in which OH or H can act as an intermediate. (C) 2003 American Institute of Physics.

Under-water scene investigation using ground penetrating radar (GPR) in the search for a sunken jet ski, Northern Ireland

A search for a submerged jet ski and the lost limb of its driver involved in a collision with a speedboat was made in a shallow lake in Northern Ireland. The location of both was crucial to establishing events at the time of the accident. Local intelligence suggested both objects were likely to be partially-buried by lacustrine silt. To avoid sediment churning, this required non-invasive, completely non-destructive assessment and mapping of the scene. A MALA RAMAC ground-penetrating radar system (GPR) mounted on floats for surveying from walkways and jetties or placed in a small rubber dinghy for offshore profiling was used. A grid was established and each line surveyed with 100, 200 and 400MHz antennae. In waters over 6m deep GPR data showed the form of the lake floor but excessive ringing occurred in the data. In waters less than 6m deep ringing diminished on both 100 and 200MHz data, the latter displaying the best trade-off between depth penetration and horizontal object resolution. 400MHz data failed to be of use in waters over 2m deep and at these depths showed only limited improvement of image quality compared to 200MHz data. Surface objects such as a wooden walkway caused interference on 200 and 400MHz data when antennae were oriented both normal and parallel to survey direction; this may be a function of the low attenuation of radar waves in freshwater, allowing excellent lateral and vertical radar wave penetration. On 200MHz data the damaged jet-ski was clearly imaged in a location that contradicted the speedboat driver's account of the accident.

‘A system that works for the sea’? Exploring Stakeholder Engagement in Marine Spatial Planning

This paper aims to contribute to the current debate on Marine Spatial Planning (MSP) by exploring the issue of stakeholder engagement. MSP is an emergent policy field that is subject to an increasing body of research, yet the role, scope and nature of participatory engagement within the process remains a neglected topic. This paper briefly reviews the nature of the ‘marine problem’, to which MSP is seen to be the response and describes the emergence of MSP policy in the UK with specific emphasis on participatory aspects. Drawing on the experience of terrestrial planning it discusses the potential benefits of stakeholder engagement in MSP and highlights some of the key issues that need to be taken into account when shaping stakeholder input into the process. It then goes on to describe the findings from a series of interviews with key stakeholders in the Irish Sea Region, which suggest that we need to develop a more critical and deeper understanding of how various interests frame the ‘marine problem’, and how they see their role in shaping the form of the MSP process. This highlights the importance of encouraging stakeholder involvement in MSP, the need to develop a shared vision of a ‘sea interest’. Priorities are then set for research to support this important policy agenda.

The cost of water from an autonomous wave-powered desalination plant

A techno-economic model of an autonomous wave-powered desalination plant is developed and indicates that fresh water can be produced for as little as £0.45/m3. The advantages of an autonomous wave-powered desalination plant are also discussed indicating that the real value of the system is enhanced due to its flexibility for deployment and reduced environmental impact. The modelled plant consists of the Oyster wave energy converter, conventional reverse osmosis membranes and a pressure exchanger–intensifier for energy recovery. A time-domain model of the plant is produced using wave-tank experimentation to calibrate the model of Oyster, manufacturer's data for the model of the reverse osmosis membranes and a hydraulic model of the pressure exchanger–intensifier. The economic model of the plant uses best-estimate cost data which are reduced to annualised costs to facilitate the calculation of the cost of water. Finally, the barriers to the deployment of this technology are discussed, but they are not considered insurmountable.

An autonomous wave-powered desalination system

The potential for an autonomous wave-powered desalination system is considered and it is identified that the most promising configuration is a reverse osmosis (RO) plant utilising a pressure exchanger-intensifier for energy recovery. A numerical model of the RO plant with a pressure exchanger-intensifier is developed that shows that a specific energy consumption of less than 2.0 kW h/m3 over a wide range of sea-water feed conditions, making it particularly suitable for use with a variable power source such as wave energy. A numerical model of the combined wave-power and desalination plant is also developed that shows that it is possible to supply the desalination plant with sea-water directly pressurised by the wave energy converter, eliminating the cost and energy losses associated with converting the energy into electricity and back to pressurised water. For a typical sea-state the specific hydraulic energy consumption of the desalination plant is estimated to be 1.85 kW h/m3 whilst maintaining a recovery-ratio of less than 25 to 35% to avoid the need for chemical pre-treatment to eliminate scaling problems. It is suggested that the economic potential for wave-powered desalination depends on these energy and cost savings more than compensating for the reduction in membrane life that occurs with variable feed conditions.

On the solubilization of water with ethanol in hydrophobic hexafluorophosphate ionic liquids

The solubility of water in the hydrophobic 1-alkyl-3-methylimidazolium hexafluorophosphate (alkyl = butyl, hexyl, and octyl) ionic liquids, can be significantly increased in the presence of ethanol as a co-solute. 1-Hexyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium hexafluorophosphate are completely miscible with ethanol, and immiscible with water, whereas 1-butyl-3-methylimidazolium hexafluorophosphate is totally miscible with aqueous ethanol only between 0.5-0.9 mole fraction ethanol at 25degreesC. At higher and lower mole fraction of ethanol, the aqueous and IL components are only partially miscible and a biphasic system is obtained upon mixing equal volumes of the IL and aqueous ethanol. The observation of a large range of total miscibility between water and the IL in the three-component system has important implications for purifications and separations from IL.

The persistence of the HgCl2 molecule in five new compounds in the system (NH4)(w)HgxCly(H2O)(z) with w : x : y : z=1 : 5 : 11 : 0, 2 : 3 : 8 : 1, 4 : 3 : 10 : 2, 2 : 1 : 4 : 1, and 10 : 3 : 16 : 0

Five new compounds in the system (NH4)Cl/HgCl2/H2O have been obtained as colourless single crystals, (NH4)Hg5Cl11, (NH4)(2)Hg3Cl8(H2O), (NH4)(4)Hg3Cl10(H2O)(2), (NH4)(2)HgCl4(H2O), and (NH4)(10)Hg3Cl16. In all of these, as in HgCl2 itself, (almost) linear HgCl2 molecules persist with Hg-Cl distances varying from 229 to 236 pm. In (NH4)(10)Hg3Cl16 there are also tetrahedra [HgCl4] with d(Hg-Cl) = 247 pm present. If larger Hg-Cl distances (of up to 340 pm) are considered as belonging to the coordination sphere of Hg-II, the structures may be described as consisting of isolated octahedra and tetrahedra as in (NH4)(10)Hg3Cl16, edge-connected chains as in (NH4)(2)HgCl4(H2O), edge-connected chains and layers of octahedra as in (NH4)(4)Hg3Cl10(H2O)(2), corrugated layers of edge-connected octahedra as in (NH4)(2)Hg3Cl8(H2O), and, finally, a three-dimensional network of connected six- and seven-coordinate Hg-Cl polyhedra as in (NH4)Hg5Cl11. The water molecules are never attached to Hg-II. The (NH4)(+) cations, and sometimes Cl- anions, play a role for electroneutrality only.

Comparison of a novel spray congealing procedure with emulsion-based methods for the micro-encapsulation of water-soluble drugs in low melting point triglycerides

The particle size characteristics and encapsulation efficiency of microparticles prepared using triglyceride materials and loaded with two model water-soluble drugs were evaluated. Two emulsification procedures based on o/w and w/o/w methodologies were compared to a novel spray congealing procedure. After extensive modification of both emulsification methods, encapsulation efficiencies of 13.04% tetracycline HCl and 11.27% lidocaine HCl were achievable in a Witepsol (R)-based microparticle. This compares to much improved encapsulation efficiencies close to 100% for the spray congealing method, which was shown to produce spherical particles of similar to 58 mu m. Drug release studies from a Witepsol (R) formulation loaded with lidocaine HCl showed a temperature-dependent release mechanism, which displayed diffusion-controlled kinetics at temperatures similar to 25 degrees C, but exhibited almost immediate release when triggered using temperatures close to that of skin. Therefore, such a system may find application in topical semi-solid formulations, where a temperature-induced burst release is preferred.

Limitations of instantaneous water quality sampling in surface-water catchments: Comparison with near-continuous phosphorus time-series data.

The validity of load estimates from intermittent, instantaneous grab sampling is dependent on adequate spatial coverage by monitoring networks and a sampling frequency that re?ects the variability in the system under study. Catchments with a ?ashy hydrology due to surface runoff pose a particular challenge as intense short duration rainfall events may account for a signi?cant portion of the total diffuse transfer of pollution from soil to water in any hydrological year. This can also be exacerbated by the presence of strong background pollution signals from point sources during low flows. In this paper, a range of sampling methodologies and load estimation techniques are applied to phosphorus data from such a surface water dominated river system, instrumented at three sub-catchments (ranging from 3 to 5 km2 in area) with near-continuous monitoring stations. Systematic and Monte Carlo approaches were applied to simulate grab sampling using multiple strategies and to calculate an estimated load, Le based on established load estimation methods. Comparison with the actual load, Lt, revealed signi?cant average underestimation, of up to 60%, and high variability for all feasible sampling approaches. Further analysis of the time series provides an insight into these observations; revealing peak frequencies and power-law scaling in the distributions of P concentration, discharge and load associated with surface runoff and background transfers. Results indicate that only near-continuous monitoring that re?ects the rapid temporal changes in these river systems is adequate for comparative monitoring and evaluation purposes. While the implications of this analysis may be more tenable to small scale ?ashy systems, this represents an appropriate scale in terms of evaluating catchment mitigation strategies such as agri-environmental policies for managing diffuse P transfers in complex landscapes.

Non-aqueous silicone elastomer gels as a vaginal microbicide delivery system for the HIV-1 entry inhibitor maraviroc

Aqueous semi-solid polymeric gels, such as those based on hydroxyethylcellulose (HEC) and polyacrylic acid (e.g. Carbopol®), have a long history of use in vaginal drug delivery. However, despite their ubiquity, they often provide sub-optimal clinical performance, due to poor mucosal retention and limited solubility for poorly water-soluble actives. These issues are particularly pertinent for vaginal HIV microbicides, since many lead candidates are poorly water-soluble and where a major goal is the development of a coitally independent, once daily gel product. In this study, we report the use of a non-aqueous silicone elastomer gel for vaginal delivery of the HIV-1 entry inhibitor maraviroc. In vitro rheological, syringeability and retention studies demonstrated enhanced performance for silicone gels compared with a conventional aqueous HEC gel, while testing of the gels in the slug model confirmed a lack of mucosal irritancy. Pharmacokinetic studies following single dose vaginal administration of a maraviroc silicone gel in rhesus macaques showed higher and sustained MVC levels in vaginal fluid, vaginal tissue and plasma compared with a HEC gel containing the same maraviroc loading. The results demonstrate that non-aqueous silicone gels have potential as a formulation platform for coitally independent vaginal HIV microbicides.

Technical Note: Assessing a 24/7 solution for monitoring water quality loads in small river catchments

Quantifying nutrient and sediment loads in catchments is dif?cult owing to diffuse controls related to storm hydrology. Coarse sampling and interpolation methods are prone to very high uncertainties due to under-representation of high discharge, short duration events. Additionally, important low-?ow processes such as diurnal signals linked to point source impacts are missed. Here we demonstrate a solution based on a time-integrated approach to sampling with a standard 24 bottle autosampler con?gured to take a sample every 7 h over a week according to a Plynlimon design. This is evaluated with a number of other sampling strategies using a two-year dataset of sub-hourly discharge and phosphorus concentration data. The 24/7 solution is shown to be among the least uncertain in estimating load (inter-quartile range: 96% to 110% of actual load in year 1 and 97% to 104% in year 2) due to the increased frequency raising the probability of sampling storm events and point source signals. The 24/7 solution would appear to be most parsimonious in terms of data coverage and certainty, process signal representation, potential laboratory commitment, technology requirements and the ability to be widely deployed in complex catchments.

Intelligent demand response electric water heating to integrate wind power in Ireland

Dwindling fossil fuel resources and pressures to reduce greenhouse gas (GHG) emissions will result in a more diverse range of generation portfolios for future electricity systems. Irrespective of the portfolio mix the overarching requirement for all electricity suppliers and system operators is that supply instantaneously meets demand and that robust operating standards are maintained to ensure a consistent supply of high quality electricity to end-users. Therefore all electricity market participants will ultimately need to use a variety of tools to balance the power system. Thus the role of demand side management (DSM) with energy storage will be paramount to integrate future diverse generation portfolios. Electric water heating (EWH) has been studied previously, particularly at the domestic level to provide load control, peak shave and to benefit end-users financially with lower bills, particularly in vertically integrated monopolies. In this paper, a continuous Direct Load Control (DLC) EWH algorithm is applied in a liberalized market environment using actual historical electricity system and market data to examine the potential energy savings, cost reductions and electricity system operational improvements.

Treatment of estrogens and androgens in dairy wastewater by a constructed wetland system.

Constructed wetland systems (CWS) have been used as a low cost bio-filtration system to treat farm wastewater. While studies have shown that CWS are efficient in removing organic compounds and pathogens, there is limited data on the presence of hormones in this type of treatment system. The objective of this study was to evaluate the ability of the CWS to reduce estrogenic and androgenic hormone concentration in dairy wastewater. This was achieved through a year long study on dairy wastewater samples obtained froma surface flow CWS. Analysis of hormonal levels was performed using a solid phase extraction (SPE) sample clean-up method, combined with reporter gene assays (RGAs) which incorporate relevant receptors capable of measuring total estrogenic or androgenic concentrations as low as 0.24 ng L1 and 6.9 ng L1 respectively. Monthly analysis showed a mean removal efficiency for estrogens of 95.2%, corresponding to an average residual concentration of 3.2 ng L1 17b-estradiol equivalent (EEQ), below the proposed lowest observable effect concentration (LOEC) of 10 ng L1. However, for one month a peak EEQ concentration of 115 ng L1 was only reduced to 18.8 ng L1. The mean androgenic activity peaked at 360 ng L1 and a removal efficiency of 92.1% left an average residual concentration of 32.3 ng L1 testosterone equivalent (TEQ). The results obtained demonstrate that this type of CWS is an efficient system for the treatment of hormones in dairy wastewater. However, additional design improvements may be required to further enhance removal efficiency of peak hormone concentrations.