Eutrophication control in river-systems: an application of INCA-P to the River Lugg

The Integrated Catchments model of Phosphorus dynamics (INCA-P) was applied to the River Lugg to determine the key factors controlling delivery of phosphorus to the main channel and to quantify the relative contribution of diffuse and point sources to the in-stream phosphorus (P) load under varying hydrological conditions. The model is able to simulate the seasonal variations and inter-annual variations in the in-stream total-phosphorus concentrations. However, difficulties in simulating diffuse inputs arise due to equifinality in the model structure and parameters. The River Lugg is split into upper and lower reaches. The upper reaches are dominated by grassland and woodland, so the patterns in the stream-water total-phosphorus concentrations are typical of diffuse source inputs; application of the model leads to estimates of the relative contribution to the in-stream P load from diffuse and point sources as 9:1. In the lower reaches, which are more intensively cultivated and urbanised, the stream-water total-phosphorus concentration dynamics are influenced more by point-sources; the simulated relative diffuse/point contribution to the in-stream P load is 1: 1. The model set-up and simulations are used to identify the key source-areas of P in the catchment, the P contribution of the Lugg to the River Wye during years with contrasting precipitation inputs, and the uptake and release of P from within-reach sediment. In addition, model scenarios are run to identify the impacts of likely P reductions at sewage treatment works on the in-stream soluble-reactive P concentrations and the suitability of this as a management option is assessed for reducing eutrophication.

Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes

Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me3SiC CC6F5 and RuCl(dppe)Cp'[Cp' = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C CC6F5)(dppe)Cp'[Cp' = Cp (2); Cp* (3)], which are related to the known compound Ru(C CC6F5)(PPh3)(2)Cp (1). Treatment of Me3SiC CC6F5 with Pt-2(mu-dppm)(2)Cl-2 in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt-2(mu-dppm)(2)(C CC6F5)(2) (4). The Pd(0)/Cu(I)-catalysed reactions between Au(C CC6F5)(PPh3) and Mo( CBr)(CO)(2) Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co-3(mu(3)-CBr)(mu-dppm)(CO)(7) or IC CFc [Fc = (eta(5)-C5H4)FeCp] afford Mo( CC CC6F5)(CO)(2)Tp* (5), Co-3(mu 3-CC CC6F5)(mu-dppm)(CO)(7) (6) and FcC CC CC6F5 (7), respectively. The diruthenium complexes 1,4-{Cp'(PP)RuC C}(2)C6F4 [(PP)Cp'=(PPh3)(2)Cp (8); (dppe)Cp (9); (dppe)Cp* (10)] are prepared from 1,4-(Me3SiC C)(2)C6F4 in a manner similar to that described for the monoruthenium complexes 1-3. The non-fluorinated complexes 1,4-{Cp'(PP)RuC C}(2)C6H4 [(PP)Cp' = (PPh3)(2)Cp (11); ( dppe) Cp (12); ( dppe) Cp* (13)], prepared for comparison, are obtained from 1,4-(Me3SiC C)(2)C6H4. Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes 2-3 and 8-13, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes 1, 2, 3, 6 and 10.

Deprotection, tethering, and activation of a one-legged metalloporphyrin on a chemically active metal surface: NEXAFS, Synchrotron XPS, and STM study of [SAc]P-Mn(III)Cl on Ag(100)

The structural and reactive properties of the acetyl-protected "one-legged" manganese porphyrin [SAc]P-Mn(III)Cl on Ag(100) have been studied by NEXAFS, synchrotron XPS and STM Spontaneous surface-mediated deprotection occurs at 300 K accompanied by spreading of the resulting thio-tethered porphyrin across the metal surface Loss of the axial chlorine ligand occurs at 498 K, without any demetalation of the macrocycle, leaving the Mn center in a low co-ordination state At low coverages the macrocycle is markedly tilted toward the silver surface, as is the phenyl group that forms part of the tethering "leg". In the monolayer region a striking transition occurs whereby the molecule rolls over, preserving the tilt angle of the phenyl group, strongly increasing that of the macrocycle, decreasing the apparent height of the molecule and decreasing its footprint, thus enabling closer packing These findings are in marked contrast with those previously reported for the corresponding more rigidly bound four-legged porphyrin [Turner, M., Vaughan, O. P. H., Kyriakou, G., Watson, D. J., Scherer, L. J; Davidson, G J. E, Sanders, J. K. M.; Lambert, R. M J. Am. Chem Soc 2009, 131, 1910] suggesting that the physicochemical :)properties and potential applications of these versatile systems should be strongly dependent on the mode of tethering to the surface.

Transition metal-directed self-assembly of calix[4]arene based dithiocarbamate ligands

The transition metal-directed self-assembly of dithiocarbamate ligand functionalised upper and lower rim calix[4]arenes affords novel dimeric bimetallic bis(calix[4]arene) species as determined by a combination of analytical methods including X-ray crystallography. An exception is a zinc(II) dithiocarbamate upper rim calix[4]arene assembly which is monomeric in nature. Electrochemical investigations reveal the bimetallic copper(II) bis(calix[4]arene) systems can electrochemically sense dihydrogen phosphate and carboxylate anions via significant cathodic perturbations of the respective copper(II)/(III) dithiocarbamate oxidation wave.

The exclusive use of integer-order spots for LEED-IV structure analysis of adsorption systems: p(2×2)-O on Ni{111}

Two different ways of performing low-energy electron diffraction (LEED) structure determinations for the p(2 x 2) structure of oxygen on Ni {111} are compared: a conventional LEED-IV structure analysis using integer and fractional-order IV-curves collected at normal incidence and an analysis using only integer-order IV-curves collected at three different angles of incidence. A clear discrimination between different adsorption sites can be achieved by the latter approach as well as the first and the best fit structures of both analyses are within each other's error bars (all less than 0.1 angstrom). The conventional analysis is more sensitive to the adsorbate coordinates and lateral parameters of the substrate atoms whereas the integer-order-based analysis is more sensitive to the vertical coordinates of substrate atoms. Adsorbate-related contributions to the intensities of integer-order diffraction spots are independent of the state of long-range order in the adsorbate layer. These results show, therefore, that for lattice-gas disordered adsorbate layers, for which only integer-order spots are observed, similar accuracy and reliability can be achieved as for ordered adsorbate layers, provided the data set is large enough.

Introducing "ecoputation": a universal systems design process

A universal systems design process is specified, tested in a case study and evaluated. It links English narratives to numbers using a categorical language framework with mathematical mappings taking the place of conjunctions and numbers. The framework is a ring of English narrative words between 1 (option) and 360 (capital); beyond 360 the ring cycles again to 1. English narratives are shown to correspond to the field of fractional numbers. The process can enable the development, presentation and communication of complex narrative policy information among communities of any scale, on a software implementation known as the "ecoputer". The information is more accessible and comprehensive than that in conventional decision support, because: (1) it is expressed in narrative language; and (2) the narratives are expressed as compounds of words within the framework. Hence option generation is made more effective than in conventional decision support processes including Multiple Criteria Decision Analysis, Life Cycle Assessment and Cost-Benefit Analysis.The case study is of a participatory workshop in UK bioenergy project objectives and criteria, at which attributes were elicited in environmental, economic and social systems. From the attributes, the framework was used to derive consequences at a range of levels of precision; these are compared with the project objectives and criteria as set out in the Case for Support. The design process is to be supported by a social information manipulation, storage and retrieval system for numeric and verbal narratives attached to the "ecoputer". The "ecoputer" will have an integrated verbal and numeric operating system. Novel design source code language will assist the development of narrative policy. The utility of the program, including in the transition to sustainable development and in applications at both community micro-scale and policy macro-scale, is discussed from public, stakeholder, corporate, Governmental and regulatory perspectives.

A design of benchmarking method for assessing performance of e-Government systems

This paper is an initial work towards developing an e-Government benchmarking model that is user-centric. To achieve the goal then, public service delivery is discussed first including the transition to online public service delivery and the need for providing public services using electronic media. Two major e-Government benchmarking methods are critically discussed and the need to develop a standardized benchmarking model that is user-centric is presented. To properly articulate user requirements in service provision, an organizational semiotic method is suggested.

Potassium budgets in grassland systems as affected by nitrogen and drainage

The main inputs, outputs and transfers of potassium (K) in soils and swards under typical south west England conditions were determined during 1999/00 and 2000/01 to establish soil and field gate K budgets under different fertilizer nitrogen (N) (0 and 280 kg ha(-1) yr(-1)) and drainage (undrained and drained) treatments. Plots receiving fertilizer N also received farmyard manure (FYM). Potassium soil budgets ranged, on average for the two years, from -5 (+N, drained) to +9 (no N and undrained) kg K ha(-1) yr(-1) and field gate budgets from +23 (+N, drained) to +89 (+N, undrained). The main inputs and outputs to the soil K budgets were fertilizer application (65%) and plant uptake (93%). Animals had a minor effect on K export but a major impact on K recycling. Nitrogen fertilizer application and drainage increased K uptake by the grass and, with it, the efficiency of K used. It also depleted easily available soil K, which could be associated with smaller K losses by leaching.

Cropping systems, carbon sequestration and erosion in Brazil, a review

Soils represent a large carbon pool, approximately 1500 Gt, which is equivalent to almost three times the quantity stored in terrestrial biomass and twice the amount stored in the atmosphere. Any modification of land use or land management can induce variations in soil carbon stocks, even in agricultural systems that are perceived to be in a steady state. Tillage practices often induce soil aerobic conditions that are favourable to microbial activity and may lead to a degradation of soil structure. As a result, mineralisation of soil organic matter increases in the long term. The adoption of no-tillage systems and the maintenance of a permanent vegetation cover using Direct seeding Mulch-based Cropping system or DMC, may increase carbon levels in the topsoil. In Brazil, no-tillage practices (mainly DMC), were introduced approximately 30 years ago in the south in the Parana state, primarily as a means of reducing erosion. Subsequently, research has begun to study the management of the crop waste products and their effects on soil fertility, either in terms of phosphorus management, as a means of controlling soil acidity, or determining how manures can be applied in a more localised manner. The spread of no-till in Brazil has involved a large amount of extension work. The area under no-tillage is still increasing in the centre and north of the country and currently occupies ca. 20 million hectares, covering a diversity of environmental conditions, cropping systems and management practices. Most studies of Brazilian soils give rates of carbon storage in the top 40 cm of the soil of 0.4 to 1.7 t C ha(-1) per year, with the highest rates in the Cerrado region. However, caution must be taken when analysing DMC systems in terms of carbon sequestration. Comparisons should include changes in trace gas fluxes and should not be limited to a consideration of carbon storage in the soil alone if the full implications for global warming are to be assessed.

Modelling cereal root systems for water and nitrogen capture: Towards an economic optimum

A quantitative model of wheat root systems is developed that links the size and distribution of the root system to the capture of water and nitrogen (which are assumed to be evenly distributed with depth) during grain filling, and allows estimates of the economic consequences of this capture to be assessed. A particular feature of the model is its use of summarizing concepts, and reliance on only the minimum number of parameters (each with a clear biological meaning). The model is then used to provide an economic sensitivity analysis of possible target characteristics for manipulating root systems. These characteristics were: root distribution with depth, proportional dry matter partitioning to roots, resource capture coefficients, shoot dry weight at anthesis, specific root weight and water use efficiency. From the current estimates of parameters it is concluded that a larger investment by the crop in fine roots at depth in the soil, and less proliferation of roots in surface layers, would improve yields by accessing extra resources. The economic return on investment in roots for water capture was twice that of the same amount invested for nitrogen capture. (C) 2003 Annals of Botany Company.

Competition in tree row agroforestry systems. 3. Soil water distribution and dynamics

The purpose of this study was to test the hypothesis that soil water content would vary spatially with distance from a tree row and that the effect would differ according to tree species. A field study was conducted on a kaolinitic Oxisol in the sub-humid highlands of western Kenya to compare soil water distribution and dynamics in a maize monoculture with that under maize (Zea mays L.) intercropped with a 3-year-old tree row of Grevillea robusta A. Cunn. Ex R. Br. (grevillea) and hedgerow of Senna spectabilis DC. (senna). Soil water content was measured at weekly intervals during one cropping season using a neutron probe. Measurements were made from 20 cm to a depth of 225 cm at distances of 75, 150, 300 and 525 cm from the tree rows. The amount of water stored was greater under the sole maize crop than the agroforestry systems, especially the grevillea-maize system. Stored soil water in the grevillea-maize system increased with increasing distance from the tree row but in the senna-maize system, it decreased between 75 and 300 cm from the hedgerow. Soil water content increased least and more slowly early in the season in the grevillea-maize system, and drying was also evident as the frequency of rain declined. Soil water content at the end of the cropping season was similar to that at the start of the season in the grevillea-maize system, but about 50 and 80 mm greater in the senna-maize and sole maize systems, respectively. The seasonal water balance showed there was 140 mm, of drainage from the sole maize system. A similar amount was lost from the agroforestry systems (about 160 mm in the grevillea-maize system and 145 mm in the senna-maize system) through drainage or tree uptake. The possible benefits of reduced soil evaporation and crop transpiration close to a tree row were not evident in the grevillea-maize system, but appeared to greatly compensate for water uptake losses in the senna-maize system. Grevillea, managed as a tree row, reduced stored soil water to a greater extent than senna, managed as a hedgerow.