Stepwise construction of [Os6(CO)18(μ6-P)]-, a hexanuclear osmium cluster monoanion with trigonal-prismatic co-ordination for phosphorus: X-ray crystal structures of [Os6(μ-H)2(CO)20(MeCN)(μ3-PH)] and [PPh3Me][Os6(CO)18(μ6-P)]

Treatment of the labile cluster [Os3(CO)11(MeCN)] with PH3 affords the substituted product [Os3(CO)11(PH3)](1) in high yield. Subsequent reaction of (1) with Na2CO3 in MeOH, followed by acidification, gives the hydrido phosphido cluster [Os3(µ-H)(CO)10(µ-PH2)](2). When (2) is heated to 45–60 °C in the presence of [Os3(CO)11(MeCN)] a hexanuclear complex with the formulation [Os6(µ-H)2(CO)21(µ3-PH)](3) is obtained. If this reaction is repeated using [Os3(CO)10(MeCN)2] instead of [Os3(CO)11(MeCN)], an acetonitrile-containing product, [Os6(µ-H)2(CO)20(MeCN)(µ3-PH)](4), is obtained. An X-ray analysis of (4) shows that two Os3 triangular units are linked by a µ3-phosphinidene ligand, which symmetrically bridges an Os–Os edge of one triangle and is terminally co-ordinated to one Os atom of the second triangle. When (3) is treated with a weak base, such as [N(PPh3)2]Cl or [PPh3Me] Br, deprotonation to the corresponding cluster monoanion [Os6(µ-H)(CO)21(µ3-PH)]–(5) occurs. Treatment of (5) with a weak acid regenerates (3) in quantitative yield. Thermolysis of (3) leads to a closing up of the metal framework, affording the cluster [Os6(µ-H)(CO)18(µ6-P)], which readily deprotonates to give the anion [Os6(CO)18(µ6-P)]–(7) in the presence of [N(PPh3)2] Cl or [PPh3Me]Br. The same anion (7) may also be obtained by direct thermolysis of (5). An X-ray analysis of the [PPh3Me]+ salt of (7) confirms that the phosphorus occupies an interstitial site in a trigonal-prismatic hexaosmium framework, and co-ordinates to all six metal atoms with an average Os–P distance of 2.31 (1)Å. Proton and 31P n.m.r. data on all the new clusters are presented, and the position of the phosphorus resonance in the 31P n.m.r. spectrum is related to the changes in the environment of the phosphorus atom.

Antioxidant capacity and phenolic composition of different woods used in cooperage

This study has investigated the antioxidant capacity of different woods used in cooperage and the effect of the botanical species of wood on this capacity. Quercus robur and Castanea sativa were the species with the highest antioxidant capacity, due to their relatively high content of phenolic compounds. However, the phenolic content of Prunus avium samples was very low, also reflected in its antioxidant capacity. All measurements of antioxidant capacity were consistent with the content and composition of the phenolic compounds detected in the wood samples. The major contributors to the antioxidant capacity were identified as phenolic acids, including gallic, protocatechuic, p-coumaric and ellagic acid and all the ellagitannins, due to their characteristic structure.

New tools to boost butterfly habitat quality in existing grass buffer strips

There are approximately 29,000 ha of grass buffer strips in the UK under Agri-Environment Schemes; however, typically they are floristically poor and as such are of limited biodiversity value. Introducing a sown wildflower component has the potential to increase dramatically the value of these buffer strips for a suite of native species, including butterflies. This study investigates management practices aiming to promote the establishment and maintenance of wildflowers in existing buffer strips. The effectiveness of two methods used to increase the establishment of wildflowers for the benefit of native butterfly species were tested, both individually and in combination. The management practices were: (1) the application of a selective graminicide (fluazifop-P-butyl) which reduces the dominance of competitive grasses; and (2) scarification of the soil which creates germination niches for sown wildflower seeds. A wildflower seed mix consisting of nine species was sown in conjunction with the scarification treatment. Responses of wildflowers and butterflies were monitored for two years after establishment. Results indicate that the combined scarification and graminicide treatment produced the greatest cover and species richness of sown wildflowers. Butterfly abundance, species richness and diversity were positively correlated with sown wildflower species richness, with the highest values in the combined scarification and graminicide treatment. These findings have confirmed the importance of both scarification as a means of introducing wildflower seed into existing buffer strips, and subsequent management using graminicides, for the benefit of butterflies. Application of this approach could provide tools to help butterfly conservation on farmland in the future.

Contributing understanding of mitigation options for phosphorus and sediment to a review of the efficacy of contemporary agricultural stewardship measures

Experiences from the Mitigation Options for Phosphorus and Sediment (MOPS) projects, which aim to determine the effectiveness of measures to reduce pollutant loading from agricultural land to surface waters, have been used to contribute to the findings of a recent paper (Kay et al., 2009, Agricultural Systems, 99, 67–75), which reviewed the efficacy of contemporary agricultural stewardship measures for ameliorating the water pollution problems of key concern to the UK water industry. MOPS1 is a recently completed 3-year research project on three different soil types in the UK, which focused on mitigation options for winter cereals. MOPS1 demonstrated that tramlines can be the major pathway for sediment and nutrient transfer from arable hillslopes, and that although minimum tillage, crop residue incorporation, contour cultivation, and beetle banks also have potential to be cost-effective mitigation options, tramline management is the one of the most promising treatments for mitigating diffuse pollution losses, as it was able to reduce sediment and nutrient losses by 72–99% in four out of five site years trialled. Using information from the MOPS projects, this paper builds on the findings of Kay et al. to provide an updated picture of the evidence available and the immediate needs for research in this area.

Mediterranean agriculture under climate change: adaptive capacity, adaptation, and ethics

In the coming decades, the Mediterranean region is expected to experience various climate impacts with negative consequences on agricultural systems and which will cause uneven reductions in agricultural production. By and large, the impacts of climate change on Mediterranean agriculture will be heavier for southern areas of the region. This unbalanced distribution of negative impacts underscores the significance and role of ethics in such a context of analysis. Consequently, the aim of this article is to justify and develop an ethical approach to agricultural adaptation in the Mediterranean and to derive the consequent implications for adaptation policy in the region. In particular, we define an index of adaptive capacity for the agricultural systems of the Mediterranean region on whose basis it is possible to group its different sub-regions, and we provide an overview of the suitable adaptation actions and policies for the sub-regions identified. We then vindicate and put forward an ethical approach to agricultural adaptation, highlighting the implications for the Mediterranean region and the limitations of such an ethical framework. Finally, we emphasize the broader potential of ethics for agricultural adaptation policy.

Elevated atmospheric CO2 changes phosphorus fractions in soils under a short rotation poplar plantation (EuroFACE)

Future high levels of atmospheric carbon dioxide (CO2) may increase biomass production of terrestrial plants and hence plant requirements for soil mineral nutrients to sustain a greater biomass production. Phosphorus (P), an element essential for plant growth, is found in soils both in inorganic and in organic forms. In this work, three genotypes of Populus were grown under ambient and elevated atmospheric CO2 concentrations (FACE) for 5 years. An N fertilisation treatment was added in years 4 and 5 after planting. Using a fractionation scheme, total P was sequentially extracted using H2O, NaOH, HCl and HNO3, and P determined as both molybdate (Mo) reactive and total P. Molybdate-reactive P is defined as mainly inorganic but also some labile organic P which is determined by Vanado-molybdophosphoric acid colorimetric methods. Organic P was also measured to assess all plant available and weatherable P pools. We tested the hypotheses that higher P demand due to increased growth is met by a depletion of easily weatherable soil P pools, and that increased biomass inputs increases the amount of organic P in the soil. The concentration of organic P increased under FACE, but was associated with a decrease in total soil organic matter. The greatest increase in the soil P due to elevated CO2 was found in the HCl-extractable P fraction in the non-fertilised treatment. In the NaOH-extractable fraction the Mo-reactive P increased under FACE, but total P did not differ between ambient and FACE. The increase in both the NaOH- and HCl-extractable fractions was smaller after N addition. The results showed that elevated atmospheric CO2 has a positive effect on soil P availability rather than leading to depletion.We suggest that the increase in the NaOH- and HCl-extractable fractions is biologically driven by organic matter mineralization, weathering and mycorrhizal hyphal turnover.

Modelling phosphorus dynamics in multi-branch river systems: A study of the Black River, Lake Simcoe, Ontario, Canada

High rates of nutrient loading from agricultural and urban development have resulted in surface water eutrophication and groundwater contamination in regions of Ontario. In Lake Simcoe (Ontario, Canada), anthropogenic nutrient contributions have contributed to increased algal growth, low hypolimnetic oxygen concentrations, and impaired fish reproduction. An ambitious programme has been initiated to reduce phosphorus loads to the lake, aiming to achieve at least a 40% reduction in phosphorus loads by 2045. Achievement of this target necessitates effective remediation strategies, which will rely upon an improved understanding of controls on nutrient export from tributaries of Lake Simcoe as well as improved understanding of the importance of phosphorus cycling within the lake. In this paper, we describe a new model structure for the integrated dynamic and process-based model INCA-P, which allows fully-distributed applications, suited to branched river networks. We demonstrate application of this model to the Black River, a tributary of Lake Simcoe, and use INCA-P to simulate the fluxes of P entering the lake system, apportion phosphorus among different sources in the catchment, and explore future scenarios of land-use change and nutrient management to identify high priority sites for implementation of watershed best management practises.

Phosphorus flux from wetland ditch sediments

The accumulation of phosphorus (P) in the bottom sediment of field drainage ditches poses a threat to the ecology both of the ditch water and downstream water courses. We investigated the amounts, forms and internal loading of sediment-bound P along two drainage ditches that regulate water levels in a basin fen (~ 200 ha) supporting a mixture of restored wetland and drained agricultural fields. Water levels in the Lady's Drove Rhyne are currently managed to enhance the biodiversity of the wetland (Catcott Lows Reserve — an area formerly cultivated for arable crop production); whereas, the East Ditch is managed to drain adjoining land that remains under arable and livestock production. Laboratory-based chemical fractionation schemes were used to characterise the forms and potential mobility of the sediment-bound P, whilst pore-water equilibrators were employed in situ to evaluate the diffusive flux of P through the sediment–water column, and to characterise the corresponding redox conditions. Along both ditches, sediment pore-water profiles indicated conditions ranging from weakly to very reducing conditions with increasing depth, and net fluxes of P from the sediment to overlying water. P flux values ranged from 0.33 to 1.30 mg m− 2 day− 1. Both the degree of P saturation (DPS) of the sediment and NaOH extractable (Fe/Al-bound) P correlated significantly (P < 0.05) with P flux. Both in the wetland and agricultural ditches, by far the highest values for P flux were recorded at sites closest to points of drainage water entry from the corresponding, adjoining land. Although the P flux data were obtained from only a single sampling event, this study highlights the contribution of historical as well as ongoing agricultural land use on the sustained elevated P status of ditch sediments in lowland catchments.

Determining the cost of in-field mitigation options to reduce sediment and phosphorus loss

The Mitigation Options for Phosphorus and Sediment (MOPS) project investigated the effectiveness of within-field control measures (tramline management, straw residue management, type of cultivation and direction, and vegetative buffers) in terms of mitigating sediment and phosphorus loss from winter-sown combinable cereal crops using three case study sites. To determine the cost of the approaches, simple financial spreadsheet models were constructed at both farm and regional levels. Taking into account crop areas, crop rotation margins per hectare were calculated to reflect the costs of crop establishment, fertiliser and agro-chemical applications, harvesting, and the associated labour and machinery costs. Variable and operating costs associated with each mitigation option were then incorporated to demonstrate the impact on the relevant crop enterprise and crop rotation margins. These costs were then compared to runoff, sediment and phosphorus loss data obtained from monitoring hillslope-length scale field plots. Each of the mitigation options explored in this study had potential for reducing sediment and phosphorus losses from arable land under cereal crops. Sediment losses were reduced from between 9 kg ha−1 to as much as 4780 kg ha−1 with a corresponding reduction in phosphorus loss from 0.03 kg ha−1 to 2.89 kg ha−1. In percentage terms reductions of phosphorus were between 9% and 99%. Impacts on crop rotation margins also varied. Minimum tillage resulted in cost savings (up to £50 ha−1) whilst other options showed increased costs (up to £19 ha−1 for straw residue incorporation). Overall, the results indicate that each of the options has potential for on-farm implementation. However, tramline management appeared to have the greatest potential for reducing runoff, sediment, and phosphorus losses from arable land (between 69% and 99%) and is likely to be considered cost-effective with only a small additional cost of £2–4 ha−1, although further work is needed to evaluate alternative tramline management methods. Tramline management is also the only option not incorporated within current policy mechanisms associated with reducing soil erosion and phosphorus loss and in light of its potential is an approach that should be encouraged once further evidence is available.

Food restriction reverses the hyper-muscular phenotype and force generation capacity deficit of the myostatin null mouse

Food restriction has a great impact on skeletal muscle mass by inducing muscle protein breakdown to provide substrates for energy production through gluconeogenesis. Genetic models of hyper-muscularity interfere with the normal balance between protein synthesis and breakdown which eventually results in extreme muscle growth. Mutations or deletions in the myostatin gene result in extreme muscle mass. Here we evaluated the impact of food restriction for a period of 5 weeks on skeletal muscle size (i.e., fibre cross-sectional area), fibre type composition and contractile properties (i.e., tetanic and specific force) in myostatin null mice. We found that this hyper-muscular model was more susceptible to catabolic processes than wild type mice. The mechanism of skeletal muscle mass loss was examined and our data shows that the myostatin null mice placed on a low calorie diet maintained the activity of molecules involved in protein synthesis and did not up-regulate the expression of genes pivotal in ubiquitin-mediated protein degradation. However, we did find an increase in the expression of genes associated with autophagy. Surprisingly, the reduction on muscle size was followed by improved tetanic and specific force in the null mice compared to wild type mice. These data provide evidence that food restriction may revert the hyper-muscular phenotype of the myostatin null mouse restoring muscle function.