495 research outputs found

    Trajectories Of Zooplankton Recovery In The Little Rock Lake Whole‐Lake Acidification Experiment

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    Understanding the factors that affect biological recovery from environmental stressors such as acidification is an important challenge in ecology. Here we report on zooplankton community recovery following the experimental acidification of Little Rock Lake, Wisconsin, USA. One decade following cessation of acid additions to the northern basin of Little Rock Lake (LRL), recovery of the zooplankton community was complete. Approximately 40% of zooplankton species in the lake exhibited a recovery lag in which biological recovery to reference basin levels was delayed by 1–6 yr after pH recovered to the level at which the species originally responded. Delays in recovery such as those we observed in LRL may be attributable to “biological resistance” wherein establishment of viable populations of key acid-sensitive species following water quality improvements is prevented by other components of the community that thrived during acidification. Indeed, we observed that the recovery of species that thrived during acidification tended to precede recovery of species that declined during acidification. In addition, correspondence analysis indicated that the zooplankton community followed different pathways during acidification and recovery, suggesting that there is substantial hysteresis in zooplankton recovery from acidification. By providing an example of a relatively rapid recovery from short-term acidification, zooplankton community recovery from experimental acidification in LRL generally reinforces the positive outlook for recovery reported for other acidified lakes

    Underuse and Overuse of Colonoscopy for Repeat Screening and Surveillance in the Veterans Health Administration

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    Regular screening with colonoscopy lowers colorectal cancer incidence and mortality. We aimed to determine patterns of repeat and surveillance colonoscopy and identify factors associated with over- and underuse of colonoscopy

    Ce(OH)2Cl and lanthanide-substituted variants as precursors to redox-active CeO2 materials

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    The cerium(III) hydroxide chloride Ce(OH)2Cl crystallises directly as a polycrystalline powder from a solution of CeCl3·7H2O in poly(ethylene) glycol (Mn = 400) heated at 240 °C and is found to be isostructural with La(OH)2Cl, as determined from high-resolution synchrotron powder X-ray diffraction (P21/m, a = 6.2868(2) Å, b = 3.94950(3) Å, c = 6.8740(3) Å, β = 113.5120(5)°). Replacement of a proportion of the cerium chloride in synthesis by a second lanthanide chloride yields a set of materials Ce1−xLnx(OH)2Cl for Ln = La, Pr, Gd, Tb. For La the maximum value of x is 0.2, with an isotropic expansion of the unit cell, but for the other lanthanides a wider composition range is possible, and the lattice parameters show an isotropic contraction with increasing x. Thermal decomposition of the hydroxide chlorides at 700 °C yields mixed-oxides Ce1−xLnxO2−δ that all have cubic fluorite structures with either expanded (Ln = La, Gd) or contracted (Ln = Pr, Tb) unit cells compared to CeO2. Scanning electron microscopy shows a shape memory effect in crystal morphology upon decomposition, with clusters of anisotropic sub-micron crystallites being seen in the precursor and oxide products. The Pr- and Tb-substituted oxides contain the substituent in a mixture of +3 and +4 oxidation states, as seen by X-ray absorption near edge structure spectroscopy at the lanthanide LIII edges. The mixed oxide materials are examined using temperature programmed reduction in 10%H2 in N2, which reveals redox properties suitable for heterogeneous catalysis, with the Pr-substituted materials showing the greatest reducibility at lower temperature

    Incorporation of square-planar Pd2+ in fluorite CeO2 : hydrothermal preparation, local structure, redox properties and stability

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    The direct hydrothermal crystallisation at 240 °C of Pd2+-containing ceria is investigated to study the extent to which precious metal dopants may be introduced into the cubic fluorite lattice. Samples of composition Ce1−xPdxO2−δ, where 0 ≤ x ≤ 0.15 can be produced in which Pd is included within the CeO2 structure to give a linear lattice expansion. Attempts to produce higher Pd2+-substitution result in the formation of PdO as a secondary phase. Ce and Pd were determined to be in the +4 and +2 oxidation states, respectively, by X-ray absorption near edge structure, suggesting oxide deficiency as the mechanism of charge balance. Extended X-ray absorption fine structure (EXAFS) analysis at the Pd K-edge reveals that Pd2+ has local square-planar coordination, as expected, and that a structural model can fitted in which the average fluorite structure is maintained, but with Pd2+ sitting in the square faces of oxide ions present in the local cubic geometry of Ce. This model, consistent with previous modelling studies, gives an excellent fit to the EXAFS spectra, and explains the observed lattice expansion. Transmission electron microscopy analysis shows that Pd is well dispersed in the nanocrystalline ceria particles, and in situ powder XRD shows that upon heating in air the samples remain stable up to 800 °C. H2-TPR shows that Pd-substitution leads to low temperature (<200 °C) reduction of the oxide, which increases in magnitude with increasing Pd-substitution. On prolonged heating, however, the Pd is lost from the ceria lattice to give dispersed Pd metal, suggesting an inherent instability of Pd-doped CeO2

    Barriers to equity in REDD+: Deficiencies in national interpretation processes constrain adaptation to context

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    A national interpretation process involving diverse actors and interests is required to transform global environmental initiatives into policies appropriate to the national or subnational context. These processes of localising norms are critical spaces to formulate equitable pathways to environmental conservation, yet have received limited attention from policy makers and researchers. We explored national policy processes for Reducing Emissions from Deforestation and Degradation (REDD+) in Uganda and Nepal from the perspectives of ‘intermediaries’, state and civil society actors at subnational and national scale who promote the interests of various stakeholder groups. Through think-tank meetings and semi-structured interviews with a range of intermediaries, we uncovered that REDD+ implementation processes in both countries are dominated by international actors, applying a demanding administrative agenda and restricting space for deliberation. Consequently, social aspects of policy were compartmentalised, reduced to technical exercises and local equity concerns inadequately addressed in national REDD+ policies. For example, social safeguards approaches were perceived to lack substantive guidelines to promote equity. Limited national political space to criticise government policy and lack of attention to relevant evidence further restricted ability to address entrenched injustices such as status inequalities faced by marginalised groups. Although civil society organisations choose to maintain official involvement with REDD+, many expressed a possibility they would oppose REDD+ in future, or serious doubts about its design and expected outcomes. Concerns centred on lack of recognition of indigenous peoples’ and local communities’ values, identities, practices and institutions such as customary tenure systems, alongside possible detrimental impacts to decentralised forest governance regimes, well established in Nepal and emerging in Uganda. We suggest features to be enshrined in REDD+ policy for adapting national interpretation processes to become more effective spaces for empowering diverse intermediaries to negotiate and influence localisation of international norms, ultimately to promote more equitable pathways to reduced deforestation and degradation

    Synthesis and polymorphism of mixed aluminium-gallium oxides

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    DSC is grateful to the EPSRC for award of an industrial CASE studentship, partly funded by Johnson Matthey plc. SEA, DMD and JEH thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”) for funding. SEA would also like to thank the Royal Society and Wolfson Foundation for a merit award.The synthesis of a new solidsolution of the oxyhydroxide Ga5–xAlxO7(OH) isinvestigated via solvothermalreaction between gallium acetylacetonate and aluminium isopropoxide in1,4-butanediol at 240 °C. A limited compositional range 0 ≤ x ≤ 1.5 is produced, with the hexagonalunit cell parameters refined from powder X-ray diffraction (XRD) showing alinear contraction in unit cell volume with increasing Al content. Solid-state 27Aland 71Ga NMR spectroscopy show a strong preference for Ga to occupythe tetrahedral sites and Al to occupy the octahedral sites. Using isopropanolas the solvent, g-Ga2–xAlxO3defect spinel solid solutions with x ≤ 1.8 can be prepared at 240 °C in24 hours. These materials are nanocrystalline, as evidenced by their broaddiffraction profiles, but the refined cubic lattice parameter shows a linearrelationship with the Ga:Al content and solid-state NMR spectroscopy again showsa preference for Al to occupy the octahedral sites. Thermal decomposition ofthe Ga5–xAlxO7(OH)occurs via poorly ordered materials that resemble e-Ga2–xAlxO3and k-Ga2–xAlxO3,but g-Ga2–xAlxO3transforms above 750 °C to monoclinic b-Ga2–xAlxO3for 0 ≤ x ≤ 1.3 and to hexagonal a-Ga2–xAlxO3for x = 1.8, with intermediate compositions 1.3 < x < 1.8 giving mixturesof the aand b polymorphs.Solid-state NMR spectroscopy shows only the expected octahedral Al for a-Ga2–xAlxO3and, for b-Ga2–xAlxO3,the ~1:2 ratio of tetrahedral:octahedral Al is in good agreement with Rietveldanalysis of the average structures against powder XRD data. Relative energiescalculated by periodic density functional theory (DFT) confirm that there is a~5.2 kJ mol–1 penalty for tetrahedral rather than octahedral Al inGa5–xAlxO7(OH), whereas this penalty is muchlower (~2.0 kJ mol–1) for b-Ga2–xAlxO3,in good qualitative agreement with the experimental NMR spectra.PostprintPeer reviewe

    Solvothermal synthesis routes to substituted cerium dioxide materials

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    We review the solution-based synthesis routes to cerium oxide materials where one or more elements are included in place of a proportion of the cerium, i.e., substitution of cerium is performed. The focus is on the solvothermal method, where reagents are heated above the boiling point of the solvent to induce crystallisation directly from the solution. This yields unusual compositions with crystal morphology often on the nanoscale. Chemical elements from all parts of the periodic table are considered, from transition metals to main group elements and the rare earths, including isovalent and aliovalent cations, and surveyed using the literature published in the past ten years. We illustrate the versatility of this synthesis method to allow the formation of functional materials with applications in contemporary applications such as heterogeneous catalysis, electrodes for solid oxide fuel cells, photocatalysis, luminescence and biomedicine. We pick out emerging trends towards control of crystal habit by use of non-aqueous solvents and solution additives and identify challenges still remaining, including in detailed structural characterisation, the understanding of crystallisation mechanisms and the scale-up of synthesis

    Conservationists’ perspectives on poverty: an empirical study

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    1. Biodiversity conservation interventions have long confronted challenges of human poverty. The ethical foundations of international conservation, including conservation’s relationship with poverty, are currently being interrogated in animated debates about the future of conservation. However, while some commentary exists, empirical analysis of conservation practitioner perspectives on poverty, and their ethical justification, has been lacking thus far. 2. We used Q methodology complemented by more detailed qualitative analysis to examine empirically perspectives on poverty and conservation within the conservation movement, and compare these empirical discourses to positions within the literature. We sampled conservation practitioners in western headquartered organisations, and in Bolivia, China, Nepal and Uganda, thereby giving indications of these perspectives in Latin America, Asia and Africa. 3. While there are some elements of consensus, for instance the principle that the poor should not shoulder the costs of conserving a global public good, the three discourses elicited diverge in a number of ways. Anthropocentrism and ecocentrism differentiate the perspectives, but beyond this, there are two distinct framings of poverty which conservation practitioners variously adhere to. 4. The first prioritises welfare, needs and sufficientarianism, and is more strongly associated with the China, Nepal and Uganda case studies. The second framing of poverty focuses much more on the need for ‘do no harm’ principles and safeguards, and follows an internationalised human rights-oriented discourse. 5. There are also important distinctions between discourses about whether poverty is characterised as a driver of degradation, or more emphasis is placed on overconsumption and affluence in perpetuating conservation threats. This dimension particularly illuminates shifts in thinking in the 30 or so years since the Brundtland report, and reflecting new global realities. 6. This analysis serves to update, parse and clarify differing perspectives on poverty within the conservation, and broader environmental movement, in order to illuminate consensual aspects between perspectives, and reveal where critical differences remain

    Ga2.52V2.48O7.33(OH)0.67, a synthetic member of the nolanite/akdalaite-type family of oxyhydroxides containing trivalent vanadium

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    The oxyhydroxide Ga2.52V2·48O7·33(OH)0.67 is prepared by reaction between Ga metal and Na3VO4 in a 1:1 monoethanolamine:water mixture at 240 ​°C. Powder neutron diffraction shows the material to be isostructural with the minerals nolanite and akdalaite, with cations occupying tetrahedral and octahedral interstitial sites in a hexagonal close-packed array of oxide/hydroxide (P63mc, a ​= ​5.7906(2) Å, c ​= ​9.2550(5) Å). Rietveld refinement against the data shows that Ga preferentially occupies tetrahedral sites, as well as some octahedral sites, and hence all V is octahedrally coordinated. The oxidation state of vanadium is confirmed as close to V3+ using V K-edge X-ray absorption near-edge structure spectroscopy, consistent with the refined chemical composition. The material is metastable, dehydrating around 300 ​°C and then decomposing above 500 ​°C, as shown by thermogravimetric analysis and thermodiffraction. The oxide Ga2.52V2.48O8 produced after dehydration at 300 ​°C is shown to contain a larger proportion of V4+ than the parent oxyhydroxide, to ensure charge balance, but the essential hexagonal structure is maintained. Variable temperature magnetisation measurements show that although both materials appear to obey the Curie-Weiss law at high temperatures, at low temperatures the inverse susceptibility curves are non-linear. There is, however, no evidence for strong magnetic exchange and the extracted effective moments are consistent with the presence of more V3+ in the oxyhydroxide compared to the oxide
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